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THE QUANTUM

IN CHEMISTRY:
An Experimentalists View
Roger rinter
School of Chemical Sciences and Pharmacy
University of East Anglia
THE QUANTUM
IN CHEMISTRY:
An Experimentalists View
THE QUANTUM
IN CHEMISTRY:
An Experimentalists View
Roger rinter
School of Chemical Sciences and Pharmacy
University of East Anglia
Copyright 2005 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester,
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Library of Congress Cataloging-in-Publication Data:
Grinter, :oger7
The 0uantum in chemistry 1 an eperimentalistGs /ie6 H :oger Grinter7
p7 cm7
Ancludes 3i3liographical re.erences and inde7
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#7 &uantum chemistry7 27 Spectrum analysis7 ,7 &uantum measure theory7
A7 Title7
&<*?27 G-5 2005
5*#

72% I dc22
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British Library Cataloguing in Publication Data
A catalogue record .or this 3oo4 is a/aila3le .rom the British Li3rary
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This 3oo4 is printed on acid2.ree paper responsi3ly manu.actured .rom sustaina3le .orestry
in 6hich at least t6o trees are planted .or each one used .or paper production7
Contents
!re"a#e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
C$apter % The :ole o. Theory in the !hysical Sciences . . . . . . . . . . . . . . . #
#70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #
#7# What is the role o. theory in scienceJ . . . . . . . . . . . . . . . . . . . . . . . . . . #
#72 The gas la6s o. Boyle and Gay2Lussac . . . . . . . . . . . . . . . . . . . . . . . . . ,
#7, An a3solute Kero o. temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *
#7* The gas e0uation o. 8an der Waals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
#75 !hysical la6s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
#7? La6s, postulates, hypotheses, etc7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?
#7- Theory at the end o. the #$th century . . . . . . . . . . . . . . . . . . . . . . . . . . -
#7% Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %
C$apter & Drom Classical to &uantum Cechanics . . . . . . . . . . . . . . . . . . . . $
270 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $
27# The motion o. the planets1 Tycho Brahe and >epler . . . . . . . . . . . . . . . #0
272 ;e6ton, Lagrange and 9amilton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##
27, The po6er o. classical mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2
27* The .ailure o. classical physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2
275 The 3lac423ody radiator and !lanc4Gs 0uantum hypothesis . . . . . . . . . . . #,
2757# !lanc4Gs solution to the 3lac423ody radiation pro3lem . . . . . . . . #5
27572 A 0ualitati/e interpretation o. the .orm o. the 3lac423ody
emission cur/e in the light o. !lanc4Gs hypothesis . . . . . . . . . . #?
2757, &uantisation in classical mechanics . . . . . . . . . . . . . . . . . . . . . #%
27? The photoelectric e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
27?7# 'insteinGs theory o. the photoelectric e..ect conLrmed
eperimentally . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
27- The emission spectra o. atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2,
27-7# BohrGs theory o. the structure o. the hydrogen atom . . . . . . . . . 2*
27-72 Comparison o. BohrGs model 6ith eperiment . . . . . . . . . . . . . 2?
27-7, Durther de/elopment o. BohrGs theory . . . . . . . . . . . . . . . . . . . 2?
27% de BroglieGs proposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?
27$ The SchroM dinger e0uation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%
27$7# 'igen.unctions and eigen/alues . . . . . . . . . . . . . . . . . . . . . . . . 2$
/i Contents
27#0 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0
!ro3lems .or Chapter 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*
C$apter ' The Application o. &uantum Cechanics . . . . . . . . . . . . . . . . . . . ,-
,70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,%
,7# "3ser/a3les, operators, eigen.unctions and eigen/alues . . . . . . . . . . . . . ,%
,72 The SchroM dinger method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$
,7, An electron on a ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *0
,7,7# The 9amiltonian operator .or the electron on a ring . . . . . . . . . *0
,7,72 Solution o. the SchroM dinger e0uation . . . . . . . . . . . . . . . . . . . . *#
,7,7, The accepta3le eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . *#
,7* 9uM c4elGs (*N
+
2+ rule1 aromaticity . . . . . . . . . . . . . . . . . . . . . . . . . . . **
,75 ;ormalisation and orthogonality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *?
,7? An electron in a linear 3o . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *?
,7?7# The 9amiltonian operator .or an electron in a linear 3o . . . . . *?
,7?72 The accepta3le eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . *-
,7?7, Boundary conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *%
,7- The linear and angular momenta o. electrons conLned 6ithin a
one2dimensional 3o or on a ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *%
,7-7# The linear momentum o. an electron in a 3o . . . . . . . . . . . . . . *$
,7-72 The angular momentum o. an electron on a ring . . . . . . . . . . . . 50
,7% The eigen.unctions o. di..erent operators . . . . . . . . . . . . . . . . . . . . . . . . 52
,7$ 'igen.unctions, eigen/alues and eperimental measurements . . . . . . . . . 5,
,7#0 Core a3out measurement1 the 9eisen3erg uncertainty principle . . . . . . . 55
,7## The commutation o. operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-
,7#2 Com3inations o. eigen.unctions and the superposition o. states . . . . . . . 5%
,7#, "perators and their .ormulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,7# !osition or co2ordinate, x . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,72 !otential energy, V

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,7, Linear momentum, p

x
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#,7* >inetic energy, W

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#,75 Angular momentum, L

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#* Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#5 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?#
!ro3lems .or Chapter , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -#
C$apter ( Angular Comentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -,
*70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -,
*7# Angular momentum in classical mechanics . . . . . . . . . . . . . . . . . . . . . . -,
*72 The conser/ation o. angular momentum . . . . . . . . . . . . . . . . . . . . . . . . -5
Contents /ii
*7, Angular momentum as a /ector 0uantity . . . . . . . . . . . . . . . . . . . . . . . . -5
*7* "r3ital angular momentum in 0uantum mechanics . . . . . . . . . . . . . . . . . -?
*7*7# The /ector model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . --
*75 Spin angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -%
*7? Total angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -%
*7?7# The addition and conser/ation o. angular momentum in
0uantum mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -$
*7?72 The la6s o. 0uantum2mechanical angular momentum . . . . . . . . %#
*7- Angular momentum operators and eigen.unctions . . . . . . . . . . . . . . . . . %2
*7-7# The raising and lo6ering, shi.t or ladder operators . . . . . . . . . . %2
*7% ;otation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %,
*7$ Some eamples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %*
*7#0 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %?
!ro3lems .or Chapter * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $,
C$apter ) The Structure and Spectroscopy o. the Atom . . . . . . . . . . . . . . . $5
570 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $?
57# The eigen/alues o. the hydrogen atom . . . . . . . . . . . . . . . . . . . . . . . . . $?
572 The 6a/e .unctions o. the hydrogen atom . . . . . . . . . . . . . . . . . . . . . . . $-
5727# The radial .unction, R
nl
!r " . . . . . . . . . . . . . . . . . . . . . . . . . . . $%
57272 The angular .unctions,
lm
!# " and
m
!$" . . . . . . . . . . . . . . . . $$
57, !olar diagrams o. the angular .unctions . . . . . . . . . . . . . . . . . . . . . . . . #00
57,7# The s2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0#
57,72 The %2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0#
57,7, The d 2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0,
57* The complete or3ital 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . #0*
575 "ther one2electron atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0*
57? 'lectron spin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #05
57- Atoms and ions 6ith more than one electron . . . . . . . . . . . . . . . . . . . . . #05
57-7# The sel.2consistent Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0?
57-72 'lectron correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0?
57-7, The periodic ta3le o. the elements . . . . . . . . . . . . . . . . . . . . . . #0-
57% The electronic states o. the atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0-
57%7# The L/e 0uantum num3ers o. a single electron . . . . . . . . . . . . . #0%
57%72 &uantum num3ers .or the many2electron atom . . . . . . . . . . . . . #0%
57%7, The assignment o. term sym3ols . . . . . . . . . . . . . . . . . . . . . . . #0%
57%7* Term energies and 9undGs rules . . . . . . . . . . . . . . . . . . . . . . . . ##0
57$ Spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ###
57$7# :ussell I Saunders or LS coupling . . . . . . . . . . . . . . . . . . . . . . ###
57$72 && coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##2
57$7, Antermediate coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##,
57$7* Anter2electronic spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . . ##5
57#0 Selection rules in atomic spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . ##5
57#07# Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##5
57#072 !arity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##?
/iii Contents
57## The Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##-
57##7# The normal Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##%
57##72 The anomalous Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . . #20
57#2 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2#
!ro3lems .or Chapter 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2$
C$apter * The Co/alent Chemical Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . #,#
?70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #,2
?7# The 3inding energy o. the hydrogen molecule . . . . . . . . . . . . . . . . . . . . #,,
?72 The 9amiltonian operator .or the hydrogen molecule . . . . . . . . . . . . . . . #,*
?7, The Born I "ppenheimer approimation . . . . . . . . . . . . . . . . . . . . . . . . . #,?
?7* 9eitler and London1 The /alence 3ond (8B+ model . . . . . . . . . . . . . . . . #,-
?75 9und and Culli4en1 the molecular or3ital (C"+ model . . . . . . . . . . . . . #,$
?7? Ampro/ing the 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7?7# The /alue o. N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7?72 !olarisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7- =niLcation1 Aonic structures and conLguration interaction . . . . . . . . . . . #*#
?7% 'lectron correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*,
?7$ Bonding and anti3onding C"s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*5
?7#0 Why is there no 9e I 9e BondJ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*?
?7## Atomic or3ital o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*?
?7##7# ' (sigma+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*-
?7##72 ( (pi+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*-
?7##7, ) (delta+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*%
?7##7* ;on23onding o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*%
?7#2 The 9omonuclear diatomic molecules .rom lithium to Ouorine . . . . . . . #*$
?7#, 9eteronuclear diatomic molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5#
?7#* Charge distri3ution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#5 9y3ridisation and resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#57# 9y3ridisation1 !auling #$,# . . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#572 9y3ridisation and the /alence 3ond theory . . . . . . . . . . . . . . . . #5?
?7#57, 9y3ridisation o. car3on A"s . . . . . . . . . . . . . . . . . . . . . . . . . . #5?
?7#57* The choice o. hy3rid or3itals . . . . . . . . . . . . . . . . . . . . . . . . . . #?#
?7#575 The properties o. hy3rid2or3ital 3onds . . . . . . . . . . . . . . . . . . . #?2
?7#? :esonance and the /alence 3ond theory . . . . . . . . . . . . . . . . . . . . . . . . #?,
?7#- Colecular geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?,
?7#-7# The /alence2shell electron2pair repulsion (8S'!:+ model . . . . . #?*
?7#-72 The 8S'!: model and multiple 3onds . . . . . . . . . . . . . . . . . . . #?5
?7#% Computational de/elopments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?-
?7#$ Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?%
!ro3lems .or Chapter ? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #-?
C$apter + Bonding, Spectroscopy and Cagnetism in Transition2Cetal
Complees . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%#
-70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%#
Contents i
-7# 9istorical de/elopment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%2
-72 The crystal Leld theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%2
-7, The electronic energy le/els o. transition2metal complees . . . . . . . . . .
-7,7# The 6ea42Leld scheme .or d
2
(eample o.
,
D in an octahedral
#%-
Leld+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%$
-7,72 The 6ea42Leld scheme .or d
2
(inclusion o.
,
!+ . . . . . . . . . . . . .
-7,7, The d
2
energy le/els .or 6ea4, strong and intermediate
#$0
octahedral Lelds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #$#
-7,7* The strong2Leld scheme .or d
2
in an octahedral Leld . . . . . . . . #$,
-7,75 Spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #$5
-7* The electronic spectroscopy o. transition2metal complees . . . . . . . . . . . #$?
-75 !airing energiesP lo62spin and high2spin complees . . . . . . . . . . . . . . . . #$-
-7? The magnetism o. transition2metal complees . . . . . . . . . . . . . . . . . . . . #$-
-7- Co/alency and the ligand Leld theory . . . . . . . . . . . . . . . . . . . . . . . . . . #$$
-7% Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20,
!ro3lems .or Chapter - . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#2
C$apter , Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#5
%70 The interaction o. radiation 6ith matter . . . . . . . . . . . . . . . . . . . . . . . . 2#?
%7# 'lectromagnetic radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#?
%7#7# The electric Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#-
%7#72 The magnetic Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#$
%72 !olarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#$
%727# Linearly polarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
%7272 Circularly polarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22#
%7, The electromagnetic spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
%7,7# Three .orms o. electromagnetic radiation . . . . . . . . . . . . . . . . . 222
%7* !hotons and their properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22,
%7*7# 8elocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22,
%7*72 'nergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*7, Cass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*7* Linear momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*75 Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%7*7? !arity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%75 Selection rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%757# The Bohr I 'instein condition . . . . . . . . . . . . . . . . . . . . . . . . . . 22?
%7? The 0uantum mechanics o. transition pro3a3ility . . . . . . . . . . . . . . . . . . 22-
%7- The nature o. the time2independent interaction $
.
|V

! y K"|$
i
. . . . . . 2,,
%7-7# The transition dipole moment . . . . . . . . . . . . . . . . . . . . . . . . . . 2,*
%7-72 The relati/e intensities o. =8 I 8AS, A: and ;C: transitions . . 2,%
%7-7, The particle and 6a/e /ie6s o. spectroscopic transitions . . . . . 2*2
%7% Spectroscopic time scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*5
%7$ &uantum electrodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*-
%7#0 Spectroscopic units and notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*-
%7#07# The energyH.re0uencyH6a/elength ais . . . . . . . . . . . . . . . . . . . 2*%
%7#072 The intensityHa3sor3ance ais . . . . . . . . . . . . . . . . . . . . . . . . . . 2*$
Contents
%7## The 'instein coe.Lcients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
%7#2 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
!ro3lems .or Chapter % . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25$
C$apter - ;uclear Cagnetic :esonance Spectroscopy . . . . . . . . . . . . . . . . . 2?#
$70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?#
$7# The magnetic properties o. atomic nuclei . . . . . . . . . . . . . . . . . . . . . . . 2?2
$72 The .re0uency region o. ;C: spectroscopy . . . . . . . . . . . . . . . . . . . . . 2?*
$7, The ;C: selection rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?*
$7* The chemical shi.t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?-
$7*7# The delta ()+ scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?%
$7*72 The shielding constant, ' (sigma+ . . . . . . . . . . . . . . . . . . . . . . 2-0
$75 ;uclear spin I spin coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-0
$7? The energy le/els o. a nuclear spin system . . . . . . . . . . . . . . . . . . . . . . 2-,
$7?7# Dirst order spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-*
$7?72 Second order spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-5
$7- The intensities o. ;C: spectral lines . . . . . . . . . . . . . . . . . . . . . . . . . . 2-?
$7% &uantum mechanics and ;C: spectroscopy . . . . . . . . . . . . . . . . . . . . . 2--
$7$ Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-%
!ro3lems .or Chapter $ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%-
C$apter %. An.rared Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%$
#070 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%$
#07# The origin o. the in.rared spectra o. molecules . . . . . . . . . . . . . . . . . . . 2$0
#072 Simple harmonic motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$0
#07, The 0uantum2mechanical harmonic oscillator . . . . . . . . . . . . . . . . . . . . 2$,
#07,7# &uantisation o. the energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$,
#07,72 Nero2point energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$*
#07,7, 8i3rational eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$*
#07* :otation o. a diatomic molecule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$*
#07*7# 'igen.unctions o. the rigid rotator . . . . . . . . . . . . . . . . . . . . . . 2$-
#075 Selection rules .or /i3rational and rotational transitions . . . . . . . . . . . . . 2$-
#0757# A semi2classical /ie6 o. the selection rules . . . . . . . . . . . . . . . ,0#
#07572 An.rared intensities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0#
#07? :eal diatomic molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,02
#07- !olyatomic molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
#07-7# ;ormal co2ordinates, normal /i3rations, /i3rational
,0,
eigen.unctions and eigen/alues . . . . . . . . . . . . . . . . . . . . . . . . ,0,
#07-72 8i3rations o. real polyatomic molecules . . . . . . . . . . . . . . . . . . ,05
#07-7, Characteristic group .re0uencies . . . . . . . . . . . . . . . . . . . . . . . . ,0%
#07-7* Large molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0%
#07% Anharmonicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0$
#07%7# Dermi resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0$
#07%72 8i3rational angular momentum and the Coriolis interaction . . . . ,##
#07$ The a*+initio calculation o. A: spectra . . . . . . . . . . . . . . . . . . . . . . . . . ,#?
##757, The t6o2electron, i7e7 electron2repulsion, energyP operator #,r
#2
,,?
##757* The total energies o. singlet and triplet state . . . . . . . . . . . . . . . ,,%
##7575 'lectron repulsion in the triplet and singlet states o. the ecited
helium atom1 a diagrammatic illustration . . . . . . . . . . . . . . . . . ,,$
##757? Summary o. Section ##75 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*#
##7? The ( 2electron spectrum o. 3enKene . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*#
##7- Selection rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,**
##7-7# 'lectron spin (multiplicity+ and transition pro3a3ility . . . . . . . . ,**
##7-72 Spatial aspects o. transition pro3a3ility .or an allo6ed electronic
transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*?
##7-7, The /i3rational .actor in the transition pro3a3ility . . . . . . . . . . . ,*-
##7% Slater determinants (Appendi ?+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*%
##7$ Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*%
!ro3lems .or Chapter ## . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*%
Contents i
#07#0 The special case o. near in.rared spectroscopy . . . . . . . . . . . . . . . . . . . ,#-
#07## Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,#-
!ro3lems .or Chapter #0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2*
C$apter %% 'lectronic Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2-
##70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2-
##7# Atomic and molecular or3itals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2%
##72 The spectra o. co/alent molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2$
##727# (

(

transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2$
##7272 n

(

transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,0
##727, Transition2metal complees . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,0
##7, Charge trans.er (CT+ spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,0
##7* Cany2electron 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,2
##75 The #s
#
2s
#
conLguration o. the helium atomP singlet and triplet states . . ,,,
##757# The energies o. the #s 2s ecited states o. the helium atom . ,,5
##7572 The one2electron energiesP operator
# 2

2

#
# 2

2

2
2,r
#
2,r
2
. . . . . . . . . . . . . . . . . . . . . . . . . ,,5
C$apter %& Some Special Topics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,5#
#270 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,52
#27# The 9uM c4el molecular or3ital (9C"+ theory . . . . . . . . . . . . . . . . . . . . . ,52
#27#7# The 3asis o. 9uM c4elGs approach . . . . . . . . . . . . . . . . . . . . . . . . ,52
#27#72 The method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,5,
#27#7, 9uM c4elGs assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,5*
#27#7* <etermination o. 9C" energies and A" coe.Lcients . . . . . . . . ,5*
#27#75 Applications o. 9C" energies . . . . . . . . . . . . . . . . . . . . . . . . . ,5-
#27#7? Applications o. 9C" coe.Lcients . . . . . . . . . . . . . . . . . . . . . . ,?#
#27#7- Some Lnal comments on the 9uM c4el theory . . . . . . . . . . . . . . . ,?2
#272 Cagnetism in chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,?,
#2727# Cagnetic suscepti3ility1 diamagnetism and paramagnetism . . . . ,?*
ii Contents
#27272 Cagnetic suscepti3ility1 .erromagnetism and anti.erromagnetism ,?5
#2727, Cagnetic Lelds and dipoles1 some deLnitions . . . . . . . . . . . . . . ,?5
#2727* The magnetic e..ect o. electronic or3ital motion . . . . . . . . . . . . ,??
#27275 The conse0uences o. chemical 3onding . . . . . . . . . . . . . . . . . . ,?%
#2727? The magnetic e..ect o. electron spin . . . . . . . . . . . . . . . . . . . . . ,?$
#2727- Cagnetism in practice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,-0
#2727% Systems o. interacting molecular magnets . . . . . . . . . . . . . . . . . ,-*
#2727$ A note o. 6arning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,-?
#2727#0 An application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,--
#27, The 3and theory o. solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,-%
#27,7# The tight 3inding approimation . . . . . . . . . . . . . . . . . . . . . . . ,-%
#27,72 The electron I gas (.ree2electron+ approimation . . . . . . . . . . . . ,%#
#27,7, Colecular and ionic solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,%?
#27,7* Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,%-
#27,75 Cetals, insulators and semiconductors . . . . . . . . . . . . . . . . . . . ,%-
#27,7? "ptical properties o. solids . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$0
#27,7- Cechanical properties o. solids . . . . . . . . . . . . . . . . . . . . . . . . ,$0
#27* Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$0
!ro3lems .or Chapter #2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$-
Appen/i#es . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
% Dundamental Constants and Atomic =nits . . . . . . . . . . . . . . . . . . . . . . . . . *0#
& The 8ariation Cethod and the Secular '0uations . . . . . . . . . . . . . . . . . . . . *0,
' 'nergies and Wa/e Dunctions 3y Catri <iagonalisation . . . . . . . . . . . . . . *##
( !ertur3ation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *#-
) The Spherical 9armonics and 9ydrogen Atom Wa/e Dunctions . . . . . . . . . *25
* Slater <eterminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *2$
+ Spherical !olar Co2ordinates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *,#
, ;um3ers1 :eal, Amaginary and Comple . . . . . . . . . . . . . . . . . . . . . . . . . . *,,
- <ipole and Transition <ipole Coments . . . . . . . . . . . . . . . . . . . . . . . . . . . *,5
%. Wa/e Dunctions .or the
,
D States o. d
2
using Shi.t "perators . . . . . . . . . . . *,$
In/ex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . **,
!re"a#e
An his prologue to Q-he .o+/et0eenG L7!7 9artley 6rote1 Q-he %ast is a foreign co1ntry2
they do things differently there7G 9e might ha/e 3een descri3ing 0uantum mechanics,
6hich goes some 6ay to eplaining 6hy it is normally only the deniKens o. that strange
land, the theoreticians, 6ho dare to enter into print a3out it7 So 6hat is a sel.2con.essed
eperimentalist doing thereJ
". the many .actors that ha/e inOuenced the de/elopment o. chemistry in the second
hal. o. the 20th century, none has 3een more important than the ineora3le di..usion across
the traditional su3@ect 3oundaries o. concepts, 6hich ha/e their origins in theoretical
physics7 Students o. chemistry and research scientists ali4e, not only in chemistry, are
under continual pressure to assimilate and apply these ideasP 0uantum mechanics .orms
a central part o. many o. them7 But the learning is hard, and although there are many
ecellent 3oo4s they tend to 3e 6ritten 3y authors 6ho are 3y nature theoreticians and
6hose approach to the su3@ect di..ers .rom that o. the eperimentalist in many 6ays7 A
4no6, 3ecause A ha/e 3een in this position all my 6or4ing li.e7
Cy original moti/ation, 6hich has not changed 6ith the years, 6as to interpret mysel.,
in as eact a 6ay as A 6as a3le, the eperimental o3ser/ations that A as a spectroscopist
6as ma4ing7 An the course o. my studies A spent a lot o. time 6ith most o. the classic tets
on the su3@ect 6hich are directed at chemists and some intended .or physicists7 Those in
the 'nglish language that is7 9o6e/er, as ecellent as they mostly are, t6o aspects o. them
o.ten .ailed to satis.y me7 Dirstly, their authors are /ery good mathematicians and do not
al6ays ma4e allo6ances .or the lesser eperience and a3ility in those realms o. people li4e
me7 This also has the un.ortunate side e..ect o. encouraging students at all le/els to 3elie/e
that their di.Lculties are attri3uta3le to a lac4 o. mathematical epertise 6hen they are, in
.act, more commonly due to a .ailure to grasp some essential 0uantum2mechanical concept7
An my eperience, once the concept has 3een grasped, the mathematical epression o. it
is much easier to understand7 Secondly, epositions o. 0uantum mechanics .re0uently
lac4 eamples o. chemical applications7 A am o. the /ie6 that a real eample, e/en 6hen
it is much simpliLed and gi/es a result 6hich does not agree 6ell 6ith eperiment, is
al6ays 3etter than no eample at all7 The tets 6hich do contain eamples are usually
those directed at a particular 3ranch o. eperimental measurement, a particular 3ranch o.
spectroscopy .or eample, and they, naturally, cannot concern themsel/es 6ith a 3roader
/ie6 o. the 0uantum mechanics 6hich they apply7 An this 3oo4 A ha/e tried to 3ring
the 3asic 0uantum2mechanical theory closer to real chemical eamples and to ma4e the
ine/ita3le mathematics in/ol/ed su3ordinate to the understanding o. the principles7
A o6e a great deal to many .riends 6ith 6hom A ha/e 6or4ed7 Cy interest in the
interpretation o. physical I chemical measurements 6as Lrst aroused 3y Stephen Cason
and continued 3y 'dgar 9eil3ronner7 When A arri/ed at the =ni/ersity o. 'ast Anglia
i/ !re.ace
(='A+ A had the great good .ortune o. entering into a period o. colla3orati/e research
6ith Andre6 Thomson 6ho 6as as determined as A to learn some 0uantum mechanics7
Together 6ith some ecellent post2doctoral .ello6s and graduate students, 6e spent many
a lunch hour che6ing literally on our pac4ed lunches and Lgurati/ely on the theory
o. groups, ligand Lelds, angular momentum, irreduci3le tensors etc7 This 6as .or me a
learning eperience li4e no other and A am in de3t to all 6ho too4 part in the struggleP
especially to Andre67
Then, as this 3oo4 3egan to gro6, A 6as most grate.ul to ;orman Sheppard 6hen
he epressed an interest in reading se/eral o. the early chapters and commenting on
them 6ith his usual, meticulous care7 A ha/e also 3eneLted .rom discussions o. particular
pro3lems 6ith many other colleagues here at ='A7 !ositi/e and encouraging suggestions
made 3y re/ie6ers o. sample chapters 6ere also much appreciated and A ha/e tried to
ta4e account o. them7
An spite o. the help A ha/e recei/ed, it is too much to hope that no errors andHor
misconceptions remain and A 6ould li4e to epand a little on that su3@ect7 ;o error in a
3oo4 .rom 6hich a reader is trying to learn something can 3e tri/ialP e/en typographical
errors can seriously mislead a student 6ho is insecure in hisHher 4no6ledge o. the su3@ect7
:eaders 6ill surely detect such errors and A 6ould 3e most grate.ul i. they 6ould in.orm
me o. them7 But misconceptions are an altogether more serious pro3lem and in this
connection A ma4e a special appeal7 An attempting to ma4e 0uantum mechanics more
approacha3le A ha/e not hesitated to simpli.y and to dra6 on classical analogies 6here/er
possi3le7 An so doing A .ear that A may ha/e /entured out on a num3er o. lim3s too 6ea4
to support the 6eight 6hich A ha/e placed upon them7 A hope that readers 6ho detect this
type o. pro3lem or 6ho .eel uneasy a3out statements 6hich A ha/e made 6ill 3e good
enough to point their concerns out to me7
A Lnal 6ord o. than4s must go to .our people7 To my parents 6ho, though they
themsel/es had only elementary educations, did e/erything they could to .urther mine7
And to my 6i.e, Charlotte, and daughter, :e3ecca, 6ho ha/e gi/en me so much support
and encouragement in my scientiLc endea/ours7 A trust that they 6ill .eel that this 3oo4
6as a 6orth6hile enterprise7
A also 6ish to than4 A/an :od6ell .or pro/ision o. the three cartoons in this 3oo47
Roger .rinter
http1HH6667grinter7o rgH0uantum7htmlH
Chapter #
T$e Role o" T$eor0
in t$e !$0si#al S#ien#es
#70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #
#7# What is the role o. theory in scienceJ . . . . . . . . . . . . . . . . . . . . . . . . . . #
#72 The gas la6s o. Boyle and Gay2Lussac . . . . . . . . . . . . . . . . . . . . . . . . . ,
#7, An a3solute Kero o. temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *
#7* The gas e0uation o. 8an der Waals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
#75 !hysical la6s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
#7? La6s, postulates, hypotheses, etc7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?
#7- Theory at the end o. the #$th century . . . . . . . . . . . . . . . . . . . . . . . . . . -
#7% Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %
%1. INTR23UCTI2N
An this chapter 6e shall consider the role o. theory in science and en0uire 6hat is meant
6hen 6e spea4 o. a Qla6G in the physical sciences7 We shall as41 6hat are these la6s, ho6
do they arise and 6hat is their /alue or purpose 6ithin scienceJ There are t6o reasons
.or approaching the su3@ect o. the 0uantum in chemistry in this 6ay7 Dirstly, these are
0uestions o. interest in their o6n right to 6hich, in my /ie6, insu.Lcient attention is
paid in the teaching o. science7 This can result in a degree o. con.usion, especially in a
su3@ect as inherently comple as 0uantum theory, 6here ne6comers to the su3@ect are apt
to thin4 that i. only they 4ne6 more mathematics they could deri/e results 6hich, in .act,
cannot 3e and ne/er 6ere deri/ed7 This leads to an undesira3le .ocus o. attention upon
the mathematical rather than the conceptual aspects o. the pro3lem7 Thus, the second
reason .or discussing scientiLc la6s is an attempt to place the la6s o. 0uantum theory
in a perspecti/e in 6hich their origin, /alue and meaning can 3e 3etter appreciated 3y
3eginners in the Leld7
%1% 4HAT IS THE R25E 26 THE2RY IN SCIENCE7
At is a matter o. historical .act that man has 3een o3ser/ing the natural 6orld, and recording
his o3ser/ations, since ancient times7 We may sa.ely conclude that the /er3al communi2
cation o. o3ser/ation is e/en older, as the times and routes o. migrating animals, 3irds
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
2 The :ole o. Theory in the !hysical Sciences
and Lsh are o. crucial importance to people 6ho li/e 3y hunting, 6hile a 4no6ledge o.
the seasons, o. rain.all etc7 is essential to .ood gatherers7
#
The importance o. these and
other natural phenomena made those 6hose 4no6ledge o. them 6as most etensi/e the
leaders o. their communities and eceptional status 6as accorded to those 6ho had, or
6ere 3elie/ed to ha/e, the a3ility to predict such e/ents7
9istorically, prediction has 3een attempted either through an appeal to the supernatural
or 3y means o. a reasoned etrapolation o. .acts already 4no6n7 These t6o approaches to
the same pro3lem are not as di..erent as they might appear7 A. an o3ser/ed .act, the annual
Oooding o. a ri/er .or eample, is 3elie/ed to 3e under the direct and immediate control
o. the gods, then it is 0uite rational to consult those gods a3out such e/ents7 ;or does
the in/ol/ement o. the supernatural necessarily conOict 6ith the ma4ing and recording o.
o3ser/ations7 At has 3een suggested that a preoccupation 6ith astrology may 6ell account
.or the .act that the Cesopotamians o. the Lrst millennium BC ecelled in astronomy7
2
Thus, the ancient .ascination 6ith the prediction o. the .uture led not only to the use o.
rite and ritual 3ut also to the recording and ordering o. o3ser/ations, a tendency 6hich
also recei/ed support .rom the 6idespread 3elie. that there must 3e a system or order
in the uni/erse7 The challenge o. Lnding this system, and o. demonstrating that one has
.ound it 3y predicting the results o. o3ser/ations yet to 3e made, is the dri/ing .orce o.
science and necessitates not only the collection o. data 3ut also the arrangement o. that
data 6ithin some conceptual .rame6or4 that ma4es it easier to remem3er, understand
and use7
We can distinguish t6o 3road categories o. such conceptual .rame6or4s, or models7
The Lrst comprises models o. an essentially descripti/e nature in 6hich the phenomenon
in 0uestion is li4ened to o3@ects o. our e/eryday eperience7 An eample o. this type
o. model 6ould 3e the description o. the .undamental constituents o. matter gi/en 3y
Lucretius, a :oman o. the Lrst century BC7 An his /ie6, all su3stances 6ere composed o.
indestructi3le atoms and . . . QThings that seem to us to 3e hard and sti.. must 3e composed
o. deeply indented and hoo4ed atoms held Lrmly 3y their intertangling 3ranches7 . . .
Li0uids, on the other hand, must o6e their Ouid consistency to component atoms that are
hard and round, .or poppy seed can 3e poured as easily as i. it 6ere 6ater . . . 7G
,
The
molecular models used 3y modern chemists .all into this categoryP atoms are represented
3y coloured spheres and 3onds 3y metal rods7
The second category o. model is the mathematical model in 6hich natural phenomena
are represented 3y a set o. sym3ols, the meanings o. 6hich ha/e 3een deLned, and 6hich
o3ey some particular rules o. mathematical manipulation7 A di..erential e0uation, .or
eample, may 3e used to model a chemical reaction 3y pro/iding a description o. the
rates o. change 6ith time o. the concentrations o. the reagents in/ol/ed in the reaction7 At
is this 4ind o. model to 6hich 6e re.er 6hen 6e spea4 o. the theoretical structure o. the
natural sciences7 At is the type o. model 6hich is most use.ul to us 6hen 6e are comparing
numerical eperimental data 6ith theoretical predictions, i7e7 in 0uantitati/e 6or47
A theoretical structure is essential to all the natural sciences7 At pro/ides the .rame6or4
into 6hich the pieces o. the @igsa6 o. eperimental data are Ltted, thus re/ealing their
inter2relationships and eposing gaps in our 4no6ledge 6hich need to 3e Llled 6ith the
results o. ne6 eperiments7 An Llling these gaps theory plays a leading roleP it not only
sho6s 6here ne6 measurements are re0uired 3ut also tells the eperimentalist 6hat to
epect 6hen the eperiments in 0uestion are per.ormed7 This is /ery important since,
The Gas La6s o. Boyle and Gay2Lussac ,
clearly, the apparatus must 3e designed so that it is capa3le o. measuring the phenomena
to 3e studied and the 0uantities used must 3e appropriate to the e0uipment7
Dor eample, suppose 6e 6ish to determine the amount o. sil/er in the 6aste solution
.rom a photographic processing la3oratory 3y precipitating insolu3le sil/er chloride 6ith
hydrochloric acid and 6eighing it7 "ur theory is em3odied in the chemical e0uation1
AgF !in solution" + 9Cl AgCl !precipitated" +
9F
The .ormula AgCl in this e0uation pro/ides the in.ormation 6here3y the amount o.
sil/er in the precipitated sil/er chloride can 3e determinedP pro/ided, o. course, that 6e
4no6 the relati/e atomic masses o. sil/er and chlorine7 The 6hole e0uation allo6s us to
calculate ho6 much sil/er chloride 6ill 3e .ormed .or a gi/en amount o. sil/er in the
a0ueous miture7 This in.ormation is re0uired not only to determine the amount o. sil/er,
3ut also to plan the eperiment in such a 6ay that the precipitate to 3e 6eighed is o. a
mass appropriate .or the chemical 3alance 6ith 6hich 6e propose to 6eigh it7 To do this
6e may need to ma4e a preliminary estimate o. the amount o. sil/er in the 6aste7
When, using a more ela3orate eample, 6e say that the length o. the "I9 3ond
in the 6ater molecule is $5.- #0
#2
m and the 9"9 3ond angle #0*75

, then
these
Lgures ha/e 3een o3tained using a theory, 0uantum mechanics in .act, 6hich relates
the measured a3sorption 3y 6ater /apour o. electromagnetic radiation in the micro6a/e
region (6a/elengths o. the order o. # I 2 cm+ to the masses o. the nuclei and the
molecular geometry7 Theory is not simply a su3stitute .or eperiment, it is a /ital
ad@unct to it7
But theory is al6ays a suggestion or hy%othesis, the correctness, or other6ise, o. 6hich
can only 3e tested against eperimental .act7 There.ore, theory must al6ays 3e su3ordinate
to eperiment7 A., a.ter thorough chec4ing .or errors, the results o. an eperiment are
.ound to di..er .rom those predicted 3y theoretical calculations, then the theory must 3e
amended, or perhaps e/en discarded7 Thus, although the theoretical .rame6or4 o. science
is an essential aspect 6hich guides our progress to6ards a deeper understanding, 6e must
al6ays recognise that a current theory may one day pro/e to 3e inade0uate and re0uire
replacement7 These points can 3e illustrated 3y means o. the gas la6s7
%1& THE AS 5A4S 26 82Y5E AN3 AY95USSAC
An #??2 :o3ert Boyle (#?2- I #?$#+ pu3lished the results o. a series o. eperiments on
the compression o. air in the closed, short arm o. a J2shaped tu3e7 Boyle o3ser/ed that as
the pressure, P , measured 3y the di..erence o. height o. the columns o. mercury in the
t6o arms o. the tu3e, increased, the /olume, V , o. air in the closed end o. the tu3e
decreased7 Durther, he noted that at constant tem%erat1re the vol1me is inversely
%ro%ortional to the %ress1re, a 0uantitati/e result 6hich could 3e epressed in the simple
e0uation1
P #,V or PV = constant !#.2.#"
The 6ords in italics and '0uation (#727#+ are 3oth epressions o. 6hat 6e no6 4no6
as BoyleGs la6, and in ans6er to t6o o. the 0uestions posed a3o/e 6e may say that
BoyleGs la6 arose .rom o. a series o. eperiments and that it epresses the results o.
those eperiments in a con/enient and precise mathematical .orm7
The dependence o. the /olume o. a gas upon temperature, t , at constant pressure 6as
studied 3y .our Drench scientists, Guillaume Amontons (#??, I #-05+, Jac0ues
Charles
* The :ole o. Theory in the !hysical Sciences
V = V
0
ep(tH2-,+
V = V
0
(# + tH2-,+
!
r
e
s
s
u
r
e

(
V
H
V
0
+
(#-*? I #%2,+, Joseph Gay2Lussac (#--% I #%50+ and 9enri :egnault (#%#0 I #%-%+7
The result o. their la3ours is 4no6n as the la6 o. Gay2Lussac, 6hich 6as pu3lished in #%*-
3y :egnault7 9e reLned the earlier eperimental methods and epressed the la6 in the
.orm1
V = V
0
!# + t ,2-,"
!#.2.2"
Where V
0
is the /olume o. the gas at 0

C7 9ere again 6e ha/e a la6 6hich has


3een disco/ered 3y eperimental measurements and, i. 6e consider it care.ully, 6e Lnd
that it says that, at constant pressure, the /olume o. a gas increases 3y #H2-, o. its /olume
at 0

C
.or e/ery degree rise in temperature7 Clearly, '0uations (#727#+ and (#7272+ are o. great
practical /alue7 They can, .or eample, 3e used to calculate the /olumes and pressures o.
gases at high temperatures7 Such calculations are essential in the design o. industrial plant
.or chemical processes, many o. 6hich ta4e place at /ery high temperatures and pressures7
%1' AN A8S25UTE :ER2 26 TEM!ERATURE
But '0uation (#7272+ carries a .ar more .undamental message, as Amontons had realised7
As 6e decrease the temperature o. the gas 3elo6 0

C, i7e7 6hen t 3ecomes negati/e,


the
/olume o. the gas decreases7 But this process must ha/e a limit, since there is no such
thing as a negati/e /olume, and it is clear .rom '0uation (#7272+ that the limit o. Kero
/olume is reached at t = 2-,

C7 There.ore, 2-,

C must 3e the lo6est


temperature
6hich can 3e achie/ed7 We are .orced to a remar4a3le conclusionP although 6e can go
up in temperature indeLnitely, there is a clear lo6er limit7 This surprising result has 3een
su3stantiated eperimentally and a more eact Lgure .or the a3solute Kero o. temperature
is 2-,7#5

C, 6hich is the origin o. the scale o. a3solute temperature 6here


temperature,
- , is measured in degrees >el/in or >1
- !>" = t !

C" + 2-,.#5
!#.,.#"
At is interesting to note here the importance o. the accuracy o. eperimental data in
.ormulating scientiLc la6s7 The mere o3ser/ation that the /olume o. a Led 0uantity o.
270
#75
#70
075
070
?00 *00 200 0 200
5 The :ole o. Theory in the !hysical Sciences
Temperature, t (C+
6ig;re %1% 'ponential and linear temperature2/olume relationships .or a gas
!hysical La6s 5
gas decreased 6hen the temperature 6as lo6ered might not ha/e led to the concept o. an
a3solute Kero o. temperature, much less to a /alue .or it7 Changes in physical 0uantities
are .re0uently descri3ed 3y an eponential .unction and in Digure #7# it is sho6n that the
e0uation1
V = V
0
ep!t ,2-," !#.,.2"
gi/es a temperature I /olume relationship 6hich is /ery similar to that gi/en 3y '0ua2
tion (#7272+ in the region o. temperature readily accessi3le to early researchers, i7e7 20
to +#00

C7 But according to '0uation (#7,72+, the /olume o. the gas ne/er reaches Kero,
no matter ho6 lo6 the temperature7 So it 6as /itally important that the accuracy o.
:egnaultGs eperimental measurements sho6ed clearly that the relationship 3et6een the
temperature and the /olume o. a gas 6as a linear rather than an eponential one7
%1( THE AS EQUATI2N 26 VAN 3ER 4AA5S
Attempts to study Gay2LussacGs la6 do6n to /ery lo6 temperatures .ailed 3ecause the
gases all li0ueLed long 3e.ore the a3solute Kero 6as reached7 And, indeed, many gases
6ere .ound to sho6 mar4ed de/iations .rom the pressure I /olume I temperature (PV-
+ 3eha/iour descri3ed 3y Boyle and Gay2Lussac .or 6hat 3ecame 4no6n as ideal
gases 6hich o3eyed the com3ined e0uation1
PV = nR- !#.*.#"
6here R is the ideal gas constant 6hich has a /alue o. %7,# J >
#
mol
#
and n is the
num3er o. moles o. gas in the sample (# mole o. gas contains ?.022 #0
2,
molecules+7 These de/iations o. the PV- 3eha/iour o. real gases .rom the ideal could 3e
represented 3y more comple gas la6s such as that proposed 3y Johannes <ideri4
8an der Waals
(#%,- I #$2,+ in
#%-,1
!P + a, V
2
"!V *" = nR- !#.*.2"
in 6hich a and * respecti/ely are parameters that allo6 .or the attraction 3et6een the
molecules and .or the Lnite /olumes o. the molecules themsel/es7 They ha/e di..erent
/alues .or di..erent gases 6hich are .ound 3y comparing the eperimentally determined
PV- 3eha/iour o. the gas 6ith the '0uation (#7*72+7
But to descri3e 8an der WaalsG e0uation in detail 6ould de/iate too .ar .rom the central
theme o. this 3oo4 and 6e there.ore turn to a summary o. the ans6ers to the 0uestions
a3out physical la6s posed in Section #707
%1) !HYSICA5 5A4S
A physical la6 epresses, either in 6ords or in alge3raic .orm, the result 6hich is to 3e
epected o. a particular eperiment7 Thus, '0uation (#7272+ tells us 6hat /olume o. gas
6e 6ould ha/e at any temperature, t , i. its /olume at 0

C is V
0
7 Drom '0uation
(#727#+
6e can calculate either pressure or /olume, though 6e must Lrst per.orm an eperiment
to determine the /alue o. the constant .or the particular gas7 A. it is an ideal gas then the
constant is nR-, 6here n is the num3er o. moles o. gas in the sample ('0uation (#7*7#++7
? The :ole o. Theory in the !hysical Sciences
La6s arise, are disco/ered or deduced as a result o. eperimental o3ser/ations7 They
are not deri/ed 3y pure mathematical reasoning though they may 3e, and indeed /ery
.re0uently are, epressed in an alge3raic .orm7 At .ollo6s .rom this that since la6s are
.ound as a result o. eperimentation they must also stand or .all 3y the results o. any
other eperiments to 6hich they relate7 Thus the ideal gas la6 ('0uation (#7*7#++ .ailed
the test o. application to all gases, especially in the region o. lo6 temperatures andHor
high pressures7 The la6 is there.ore o. limited applica3ility7 But it is not useless and there
are many circumstances in 6hich it can pro/ide /alua3le results7
A group o. one or more la6s normally underlies a theoretical model o. some aspect
o. the real 6orld as it is seen 3y science7 Thus, the three la6s o. thermodynamics are the
.oundation stones, disco/ered 3y eperiment, 6hich allo6 us to descri3e 0uantitati/ely
the inter2con/ersion o. the /arious .orms o. energyP o. heat into mechanical 6or4 .or
eample7 Together they .orm a mathematical model o. all such processes7 ;e6tonGs three
la6s per.orm the same .unction .or mechanics, the study o. motionP in the net chapter
6e shall eamine them in more detail7
The /alue o. la6s to science and technology applies at /arious le/els7 At the most
simple, 3ut highly signiLcant in applied science, there is the practical use o. a la6 to
predict a 0uantity 6hich cannot 3e readily measuredP the gas pressure in a no/el chemical
plant 6hich is still at the planning stage, .or eample7 A la6 also esta3lishes the .rame6or4
into 6hich eperimental results may 3e Ltted as they 3ecome a/aila3le7 This not only
pro/ides the means o. interpreting the results 3ut also alerts the eperimentalist 6hen a
ne6 result cannot 3e reconciled 6ith the current structure o. the theory7 This may mean
that an eperimental error has 3een made or that the la6 is Oa6ed7 At a deeper le/el,
la6s re/eal ne6 concepts 6hich 6ere not suspected at the time 6hen the measurements
6hich ga/e rise to the la6 6ere made7 We may sa.ely assume that the concept o. an
a3solute Kero o. temperature 6as not the idea 6hich stimulated the Lrst eperiments o.
AmontonsP 3ut it arose directly .rom them7 9ere lies the great importance o. la6s .or the
de/elopment o. the natural sciences7 As the .ull signiLcance o. the 0uantities related in
a la6 is appreciated, scientists are led to a deeper understanding o. their su3@ect and to
the .ormulation o. ne6 eperiments to test the la6 at the more .undamental le/el7 A. the
la6 .ails, such a test it must 3e regarded as Oa6ed and o. limited use, 3ut not necessarily
totally useless7 The important point is that eperiment is the only test o. the /alidity o.
a la67 La6s summarise the results o. a 6ealth o. eperimental data and present them
in a condensed .orm suita3le .or application or .or .urther study7 But they are al6ays
su3ordinate to eperiment7
%1* 5A4S< !2STU5ATES< HY!2THESES< ETC1
The 6aters o. the present discussion are sometimes muddied 3y the /ariety o. terms
used to descri3e the same thing7 We spea4, .or eample, o. the gas la0s, !lanc4Gs 0uan2
tum hy%othesis, the !auli %rinci%le and the %ost1lates o. 0uantum mechanics7 'ach term
highlighted in italics has essentially the same meaningP it is a statement, 6hich 6e ha/e
here called a la6, or a set o. such statements, that summarises the results o. eperimen2
tal measurements7 The di..erent 6ords epress di..erent aspects o. the meaning o. that
statement7 The terms la0 and %rinci%le emphasise the po6er and immuta3ilityP %ost1late
and hy%othesis the .act that this is a suggestion or a proposal 6hich may later re0uire
Theory at the 'nd o. the #$th Century -
modiLcation7 But in this 3oo4 6e shall regard all such epressions, and some others, as
meaning la6s7
%1+ THE2RY AT THE EN3 26 THE %-TH CENTURY
As the #$th century dre6 to a close the theoretical 3asis o. the physical sciences appeared
to 3e /ery mature and po6er.ul7 An particular, the three great structures o. Ca6ellGs
e0uations, 6hich descri3e the 3eha/iour o. electromagnetic radiation, thermodynamics
and mechanics, 6ere remar4a3ly success.ul in interpreting the eperimental .acts then
4no6n7 Three eamples sho6 the range and po6er o. these la6s7
The la6s o. mechanics had 3een .ormulated 3y Asaac ;e6ton (#?*, I #-2-+ to model the
motions o. the planets and descri3ed these motions 6ith remar4a3le accuracy7 <uring the
#%?0s James Cler4 Ca6ell (#%,# I #%-$+ and Lud6ig 'd6ard BoltKmann (#%** I
#$0?+ used ;e6tonian mechanics to descri3e the motion o. molecules in a gas,
de/eloping 6hat 6e no6 call the 4inetic theory o. gases7 The theory is in ecellent
agreement 6ith the etensi/e eperimental data encapsulated in the gas la6s o. Boyle and
Gay2Lussac7 The many de/iations .rom the eperimentally o3ser/ed 3eha/iour o. real
gases are due to the .ailure o. other assumptions in the theoryP that there is no attracti/e
.orce 3et6een the molecules .or eample7 ;e6tonian mechanics 6as thus sho6n to 3e
applica3le to 3odies
ranging in mass 3et6een #0
25
and #0
+25
4g7
An the area o. thermodynamics, the .re0uency o. the chirping o. the tree cric4et, 4ecan+
th1s, has 3een .ound to depend upon the a3solute temperature in strict con.ormity 6ith the
e0uation Lrst put .or6ard 3y S/ante August Arrehnius (#%5$ I #$2-+7
*
The logarithm
o. the .re0uency o. chirping is in/ersely proportional to the a3solute temperature,
sho6ing that the tree cric4etGs chirping is 0uite in/oluntary and is controlled 3y its
3ody chem2 istry 6hich, in turn, is su3@ect to the la6s o. thermodynamics7 The same is
true o. the autonomous .unctions o. the higher mammalsP the human heart 3eat .or
eample, though the temperature range a/aila3le to the eperimentalist is rather small in
this case7
"ur Lnal eample concerns electricity, magnetism and light7 Cichael Daraday (#-$# I
#%?-+ had sho6n that an electric current Oo6ing in a coil produces a magnet and that
6hen polarised light passes through a glass plate surrounded 3y the magnetic coil the
plane o. polarisation o. the light is rotated7 Thus, electricity, magnetism and light are
related7 An electric current can 3e measured 3y determining the magnetism it producesP
the units o. this measurement are called electromagnetic units, emu7 An electric current
can also 3e measured in terms o. the Oo6 o. chargeP the units o. this type o. measurement
are electrostatic units, esu7 An #%5-, Gusta/ >ircho.. (#%2* I #%%-+ sho6ed
eperimentally that the ratio o. the emu to the esu 6as e0ual to the /elocity o. light7 These
relationships 3et6een electricity, magnetism and light and 3et6een the emu and the esu
6ere 3rilliantly and 0uantitati/ely interpreted 3y Ca6ell 6ith his mathematical model o.
electromagnetic radiation pu3lished in #%-,7 Ca6ellGs model, 6hich is al6ays re.erred to
as 5ax0ell6s e71ations, though they might e0ually 6ell 3e called Ca6ellGs la6s,
sho6ed that light and all 6a/elengths o. electromagnetic radiation could 3e descri3ed in
terms o. a magnetic and an electric Leld that are orientated at right2angles to each
other and oscillate 6ith the .re0uency o. the radiation7 This led to the prediction that an
oscillating electric spar4 6ould generate electromagnetic radiation, a prediction 6hich 6as
3eauti.ully conLrmed 3y 9einrich 9ertK (#%5- I #%$*+ in a series o. eperiments reported
in #%%? I #%%%7 We shall
% The :ole o. Theory in the !hysical Sciences
eplore Ca6ellGs description o. electromagnetic radiation and the properties o. polarised
light .urther in Chapter %7
With successes li4e these to its credit it seems scarcely surprising that some physicists
apparently thought that there 6as little more to do in the Leld o. theory other than to dot
some iGs and cross a .e6 tGs7 ;e/ertheless, there 6ere a small num3er o. eperiments the
results o. 6hich deLed interpretation in terms o. the theories, i7e7 la6s, then a/aila3le7 At
6as the search .or solutions to these pro3lems 6hich led to the re/olutionary ideas o. Ca
!lanc4 (#%5% I #$*-+ and Al3ert 'instein (#%-$ I #$55+, and to 0uantum mechanics7 An
the net chapter 6e shall .ollo6 the history o. mechanics to illustrate .urther the role 6hich
theory plays in science and to see ho6, early in the 20th century, some o. the .oundations
o. the structure o. theoretical physics 6ere .ound to 3e 3y no means as secure as they
had once appeared7
%1, 8I85I2RA!HY AN3 6URTHER REA3IN
#7 C7S7 Coon, -he 81nting Peo%les, !enguin Boo4s, 9armonds6orth, =>, #$-?7
27 S7D7 Cason, A 8istory of the Sciences, Collier Boo4s, ;e6 Ror4, #$?27
,7 Lucretius, -he Nat1re of the Universe, Translation 3y :7'7 Latham, !enguin Boo4s, 9armonds2
6orth, =>, #$5#7
*7 D797 Johnson, 97 'yring and J7B7 Sto/er, -he -heory of Rate Processes in /iology and 5edicine,
Wiley, ;e6 Ror4, #$-*7
Chapter 2
6rom Classi#al to Q;ant;m
Me#$ani#s
270 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $
27# The motion o. the planets1 Tycho Brahe and >epler . . . . . . . . . . . . . . . . #0
272 ;e6ton, Lagrange and 9amilton . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##
27, The po6er o. classical mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2
27* The .ailure o. classical physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2
275 The 3lac423ody radiator and !lanc4Gs 0uantum hypothesis . . . . . . . . . . . . #,
2757# !lanc4Gs solution to the 3lac423ody radiation pro3lem . . . . . . . . . . #5
27572 A 0ualitati/e interpretation o. the .orm o. the 3lac423ody emission
cur/e in the light o. !lanc4Gs hypothesis . . . . . . . . . . . . . . . . . . #?
2757, &uantisation in classical mechanics . . . . . . . . . . . . . . . . . . . . . . #%
27? The photoelectric e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
27?7# 'insteinGs theory o. the photoelectric e..ect conLrmed
eperimentally . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
27- The emission spectra o. atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2,
27-7# BohrGs theory o. the structure o. the hydrogen atom . . . . . . . . . . . 2*
27-72 Comparison o. BohrGs model 6ith eperiment . . . . . . . . . . . . . . . 2?
27-7, Durther de/elopment o. BohrGs theory . . . . . . . . . . . . . . . . . . . . 2?
27% de BroglieGs proposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?
27$ The SchroM dinger e0uation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%
27$7# 'igen.unctions and eigen/alues . . . . . . . . . . . . . . . . . . . . . . . . 2$
27#0 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0
!ro3lems .or Chapter 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*
&1. INTR23UCTI2N
An this chapter 6e shall Lrst .ollo6 the historical course o. the de/elopment o. ;e6tonian
or classical mechanics7 We do this not only 3ecause classical mechanics is a limiting case
o. 0uantum mechanics, 3ut also 3ecause the story o. ho6 classical mechanics de/eloped
is an ecellent illustration o. ho6 a set o. la6s and the theoretical model 6hich they sus2
tain de/elops as a result o. the interplay 3et6een eperiment and theory7 9a/ing arri/ed
6ith classical mechanics at the end o. the #$th century, 6e shall in/estigate some partic2
ularly important eperimental results 6hich the la6s o. thermodynamics, mechanics and
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
#0 Drom Classical to &uantum Cechanics
electromagnetic radiation that 6ere a/aila3le at that time 6ere 0uite una3le to interpret,
despite their outstanding successes in many other applications7 Dinally, 6e shall see ho6
'r6in SchroM dinger and Werner 9eisen3erg cut the Gordian 4not 6ith the introduction
o. a ne6 mechanics I 0uantum mechanics7
&1% THE M2TI2N 26 THE !5ANETS: TYCH2 8RAHE AN3 =E!5ER
Be.ore there can 3e any theory there must 3e eperimental o3ser/ations to 3e interpreted
3y the theory7 (This proposition is not sel.2e/identP the ancient Gree4s de/eloped theo2
retical concepts almost entirely 6ithout appeal to eperimental e/idence7+ The collection
o. the eperimental data 6hich .ormed the 3asis .or the Lrst theory o. mechanics may 3e
traced 3ac4 to the astronomical o3ser/ations made, 6ithout a telescope, 3y the <anish
no3leman Tycho Brahe (#5*? I #?0#+, 6hose measurements 6ere the most important
and accurate o. early modern times7 Tycho, 6ho is usually 4no6n 3y this latinised
/ersion o. his <anish name, Tyge, 6as reno6ned .or his Lery temperament and .or most
o. his li.e he 6ore an artiLcial sil/er nose to replace the original appendage 6hich had
3een sliced o.. in a duel at the age o. #$7 At is interesting to note that he thought it 6as
not possi3le to ma4e o3ser/ations 6ithout the guidance o. a theoretical system o. the
6orld, and he adopted a modiLed earth2centred system, no6 o. course, 4no6n to 3e
.alse7 But the idea that measurements should 3e made in the light o. a theory 6hich,
it is 3elie/ed, can interpret them and Lt them into the .rame6or4 o. our eisting
4no6ledge, is an important part o. the modern scientiLc methodP a point discussed in
Chapter #7
An #5$$, Tycho Brahe mo/ed .rom Copenhagen to !rague, 6here he 6as @oined 3y
German mathematical astronomer Johannes >epler (#5-# I #?,0+ in #?007 When he
died in #?0#, Tycho 3e0ueathed his collection o. data to >epler 6ho .ound, a.ter many
years o. eacting 6or4, that the o3ser/ations o. the planets could 3e interpreted in terms o.
the .ollo6ing three la6s7
Keplers La!s of Planetary "otion
#7 The or3its o. the planets are ellipses 6ith the sun at one .ocus7
27 The line dra6n .rom the sun to the planet s6eeps out e0ual areas in e0ual times7
,7 The s0uare o. the time re0uired .or a planet to complete its or3it is proportional to the
cu3e o. its mean distance .rom the sun, i7e7 the length o. the semi2ma@or ais o. the
ellipse7
These la6s are illustrated graphically in Digure 27#7
An .ormulating his la6s, >epler 3rought the science o. mechanics .rom the data2
collection phase to the net important stage through 6hich any de/eloped scientiLc theory
must pass7 This is the stage at 6hich the 4no6n eperimental data are uniLed, in that
it is sho6n that the data can 3e interpreted in terms o. a small num3er o. .undamental
concepts1 the la6s7 Clearly, i. the la6s are soundly 3ased they ha/e predicti/e po6er,
i7e7 the results o. eperiments or o3ser/ations not yet made can 3e .oretold7 This is the
only con/incing test o. the la6s7 A set o. la6s constitutes a theory, and 6hen a theory
.ails systematically to predict correctly the result o. eperiments, then that theory must
3e amended or, in etreme cases, a3andoned7
S
;e6ton, Lagrange and 9amilton ##
c
r
d 3
a
p
o
0
Sun
s
pI0 is the ma@or and rIs the minor ais o. the ellipse 6hich the path o.
the planet traces around the sun7 The or3its o. the planets o. our solar
system are much more li4e circles than that sho6n here 6hich more
closely resem3les that o. an asteroid, e7g7 Acarus7
A. the planet ta4es e0ual times to mo/e .rom a to 3 and .rom c to d then
the areas o. the t6o sectors, aIsunI3 and cIsunId, o. the ellipse are e0ual7
6ig;re &1% >eplerGs la6s o. planetary motion
The predicti/e po6er o. >eplerGs la6s is illustrated 3y his ta3les o. astronomical
data, pu3lished in #?2-, 6hich he calculated 3y means o. his three la6s and named the
R1dol%hine -a*les in honour o. his patron, the emperor :udolph AA7 The planets Cercury
and 8enus, 6hich ha/e or3its o. radius less than that o. 'arth, sometimes pass 3et6een
the earth and the sun7 At such times the planet in 0uestion, /ie6ed .rom the earth, can 3e
seen to mo/e across the .ace o. the sun7 This is 4no6n as a transit o. the planet7 With the
aid o. his ta3les, >epler correctly predicted the transits o. Cercury (-th ;o/em3er, #?,#+
and o. 8enus (*th <ecem3er, #?,$ and ?th June, #?-#+ across the sunGs disc7 All these
e/ents actually too4 place as >epler had said they 6ouldP 3ut not 3e.ore he died in #?,07
The net stage in this 3rie. history o. classical mechanics concerns a .urther phase
through 6hich scientiLc theories o.ten passP a phase in 6hich a more .undamental, and
hence more 6idely applica3le, set o. la6s is sought7 >eplerGs la6s descri3ed the motions
o. the planets I 3ut 6hy did they mo/e in that 6ayJ An ans6er to that 0uestion might
re/eal that the motions o. other 3odies 6ere go/erned 3y similar la6s7
&1& NE4T2N< 5ARANE AN3 HAMI5T2N
Asaac ;e6ton (#?*, I #-2-+ 6as not the only man o. his time to grapple 6ith this
pro3lem7 9is ans6er to it, together 6ith accounts o. many o. his other scientiLc and
mathematical achie/ements, appeared in his Philoso%hiae Nat1ralis Princi%ia 5athematica
in #?%-7 The .our la6s upon 6hich he 3ased his analysis 6ere clearly o. a much more
.undamental, and there.ore more general, nature than >eplerGs7
#e!tons La!s of "otion
#7 A particle mo/es 6ith a constant (perhaps Kero+ /elocity (and there.ore in a straight
line+ unless it is acted upon 3y a .orce7
#2 Drom Classical to &uantum Cechanics
=

27 A particle acted upon 3y a .orce (9 + 6ill mo/e 6ith an acceleration (a+ proportional
to that .orce, the constant o. proportionality 3eing the in/erse o. its mass (m+7
a = 9,m !2.2.#"
,7 When t6o particles act upon one another, the t6o .orces acting on the particles are
e0ual and opposite to one another and are directed along the line @oining the t6o
particles7
*7 The gra/itational .orce o. attraction 3et6een t6o 3odies is proportional to the product
o. their masses (m
#
and m
2
+ and in/ersely proportional to the s0uare o. the distance
(r + 3et6een them7 The constant o. proportionality is the gra/itational constant (.+7
9 .

m
#
m
2

!2.2.2"
r
2
The items or postulates # to , constitute the la6s o. 6hat 6e no6 4no6 as classical
mechanics7 <uring the .ollo6ing t6o centuries other .ormulations 3ased on di..erent
postulates 6ere de/eloped, nota3ly 3y Joseph2Louis Lagrange (#-,? I #%#,+ and
William :o6an 9amilton (#%05 I #%?5+7 9o6e/er, these later .ormulations o. classical
mechanics 6ere entirely consistent 6ith ;e6tonGs and 6ith each otherP any one /ersion
could 3e deri/ed mathematically .rom any other7 The Lagrangian and 9amiltonian
.ormulations .ound acceptance 3ecause they 6ere more elegant in certain applications
and the theory as a 6hole scored many truly remar4a3le successes7
&1' THE !24ER 26 C5ASSICA5 MECHANICS
An Section #7- attention 6as dra6n to the 6ay in 6hich Ca6ell and BoltKmann de/eloped
the 4inetic theory o. gases 3y applying ;e6tonGs la6s to the motion o. the molecules
o. a gas, there3y o3taining a deeper understanding o. the gas la6s o. Boyle, Charles
and Gay2Lussac7 The gas la6s 6ere to the study o. gases 6hat >eplerGs la6s 6ere
to mechanicsP the Lrst attempt to uni.y a mass o. eperimental data in a mathematical
.ormalism7 The 6or4 o. ;e6ton, Ca6ell and BoltKmann 3rought these t6o strands
o. theoretical physics together and classical mechanics 6as thus sho6n to 3e largely
applica3le to 3odies ranging in mass .rom #0
25
to #0
+25
4g7 "ther eamples o. the
a3ility o. theory to interpret /ery di/erse eperimental o3ser/ations ha/e 3een cited in
Chapter #7 Theoretical physicists at the end o. the #$th century 6ere .ully @ustiLed in
.eeling that their science, 6hich 6e may term classical theoretical physics, 6as capa3le
o. meeting any challenge the eperimentalist might thro6 do6n7 And yet eperimental
measurements already on record, or soon to 3e made, 6ould 3e sho6n to 3e .undamentally
at /ariance 6ith the la6s o. classical physics and 6ould, in due course, trigger a complete
re/olution in the su3@ect7 What 6ere those measurementsJ
&1( THE 6AI5URE 26 C5ASSICA5 !HYSICS
At goes 6ithout saying that so cogent and success.ul a structure as classical physics did
not .all easily or rapidly7 A. the la6s are thought o. as the 3elt o. the structure then
the 3lo6s that 3rought it do6n .ell 3elo6 that 3elt, stri4ing at .undamental assumptions
The Blac42Body :adiator and !lanc4Gs &uantum 9ypothesis #,
6hich 6ere em3odied in the la6s 3ut ne/er eplicitly stated7 The .act that the structure
needed to 3e replaced rather than simply repaired too4 many years to gain acceptance,
and the replacement 6as scarcely /ia3le until the late #$20s7 The Lrst ,0 years o. the
20th century 6as at one and the same time a period o. turmoil and o. intense ecitement
and creati/ity in the scientiLc 6orld7 At 6itnessed some o. man4indGs most outstanding
intellectual achie/ements7
There 6as one ma@or 3lo6 6hich 6e shall not discuss here7 At .ell in #$05 6hen Al3ert
'instein (#%-$ I #$55+ sho6ed that, 3ecause o. the Lnite /elocity o. light, to say that
t6o e/ents ta4e place simultaneously only has meaning i. the e/ents occur at the same
place, and the concepts o. space and time cannot there.ore 3e separated as they are in
classical physics7 'instein demonstrated that the /elocity o. light 6as a limiting /elocity
and that, although ;e6tonian mechanics 6as 0uite ade0uate .or 3odies mo/ing 6ith
/elocities only a .raction o. that o. light, it 6as not applica3le to 3odies mo/ing at
/elocities approaching that limit7 ;e/ertheless, 6e 6ould not thin4 o. using relati/istic
mechanics to calculate the or3it o. a communications satellite .or eample7 ;e6tonian
mechanics is much easier to apply and, .or such a system, gi/es ans6ers 6hich are in
practice 0uite indistinguisha3le .rom the relati/istic results7 This illustrates a /ery
important pointP although 6e 4no6 that classical mechanics is o. limited applica3ility,
it is still etremely use.ul and /ery 6idely used7
Drom the point o. /ie6 o. the de/elopment o. 0uantum mechanics, a more important
e/ent had ta4en place .our years 3e.ore 'instein proposed his theory o. relati/ity7 An #$0#
Ca >arl 'rnst Lud6ig !lanc4 (#%5% I #$*-+ proposed a similarly radical solution to
a pro3lem that had 3een plaguing theoreticians throughout the #%$0sP the energy
spectrum o. the 3lac423ody radiator7
&1) THE 85AC=9823Y RA3IAT2R AN3 !5ANC=S
QUANTUM HY!2THESIS
Any 3ody at a temperature a3o/e the a3solute Kero emits electromagnetic radiation o/er
a range o. 6a/elengths7 The energy re0uired to produce this radiation, 6hich is 4no6n
as thermal radiation, comes .rom the thermal agitation o. the particles o. 6hich the 3ody
is composed and, i. the temperature o. the 3ody is a3o/e that o. its surroundings, then,
as the radiation is emitted, the 3ody cools do6n7 When the 3ody reaches the temperature
o. its surroundings e0uili3rium is esta3lished and the 3ody a3sor3s and emits radiation
at eactly the same rates7 Both the emission and the a3sorption processes are o. interest
to us7 An #%-$ Jose. Ste.an (#%,5 I #%$,+ disco/ered eperimentally that the total
energy per second (:
-
+ emitted .rom the sur.ace o. a 3ody o/er all .re0uencies is
proportional to the .ourth po6er o. its a3solute temperature (- +1
:
-
-
*
An #%%* BoltKmann deduced the constant o. proportionality .rom thermodynamic prin2
ciples and 6rote the e0uation in the .orm1
:
-
= ' e-
*
!2.5.#" 6here ' is the Ste.an2BoltKmann constant (' = 5.?- #0
%
W m
2
>
*
+
and e is a dimensionless constant called the emissivity, 6hich lies 3et6een 0 and #,
depending upon
the nature o. the emitting sur.ace7
'
n
e
r
g
y

d
e
n
s
i
t
y

p
e
r

m
e
t
e
r

6
a
/
e
l
e
n
g
t
h

i
n
t
e
r
/
a
l

(
J

m

*
+
T
/
i
s
i
3
l
e

r
a
n
g
e
#* Drom Classical to &uantum Cechanics
The a3ility o. a 3ody to a3sor3 electromagnetic radiation is deLned 3y its a*sor%tivity,
a, 6hich is the ratio o. the total radiant energy .alling upon its sur.ace to the total
energy a3sor3ed 3y the sur.ace7 Gusta/ >irchho.. sho6ed 3y a po6er.ul thermodynamic
argument that e 6as e0ual to a, and this e0uality has also 3een su3stantiated 3y eperiment7
Thus, good a3sor3ers o. radiation are also good emitters, and /ice /ersa7 A 3ody 6hich
is 3oth a per.ect emitter and a per.ect a3sor3er, i7e7 one .or 6hich e = a = #.0 is
called
a *lac; *ody and is o. particular interest7 The 3est eperimental realisation o. a 3lac4
3ody sur.ace is a small hole in a ca/ity .urnace 6ith 3lac4ened inner 6alls7 :adiation
passing in through the hole has e..ecti/ely no chance o. 3eing reOected 3ac4 through it,
so a = #.0 and there.ore e = #.0
also7
The reason .or the great interest in the properties o. the per.ectly emitting and a3sor3ing
3lac4 3ody can 3e seen 3y setting e = #.0 in '0uation (2757#+7 The total energy
emitted is .ound to 3e dependent on the Ste.an2BoltKmann constant and the .ourth
po6er o. the
a3solute temperature 3ut not upon any aspect o. the 3ody itsel.7 Clearly, 3lac423ody
radiation is a /ery .undamental phenomenon 6hich demands an interpretation7 Accurate
eperimental data 6ere pro/ided in #%$$ 3y "tto :ichard Lummer (#%?0 I #$25+ and
'rnst !ringsheim (#%5$ I #$#-+7 They used a de/ice not unli4e a spectrometer to
measure the 6ay in 6hich the intensity o. the emitted radiation, : !<", depended upon
the 6a/elength o. that radiation, <, and .ound cur/es such as those sho6n in Digure 2727
The ordinate o. Digure 272 is not : !<" 3ut =!<", the energy density inside the ca/ity,
6hich is e0ual to
*: !<",c 6here c is the /elocity o. light7 Core precisely, =!<" is the energy o. the radiation
in the 6a/elength inter/al < to < + d< in # m
,
o. the ca/ity7 ;ote ho6 the pea4 o. the
cur/e mo/es to shorter 6a/elengths as the temperature is increased7 This phenomenon is
o3ser/ed 6hen the Llament o. an electric Lre goes .rom dull red to almost 6hite as the
Lre heats up7 Dor a particular temperature, the total energy emitted, :
-
, is proportional to
the area under the cur/e and one can see ho6 rapidly this rises 6ith temperature, as is
re0uired 3y the .actor -
*
in '0uation (2757#+7
'/en 3e.ore Lummer and !ringsheimGs accurate data 3ecame a/aila3le, the essential
.orm o. the relationship 3et6een energy and 6a/elength 6as 4no6n and had stimulated
?000
5000
- = 2000 >
=ltra/iolet catastrophe U
*000
,000
- = #-50 >
:ayleigh2Jeans
e0uation - = 2000 >
2000
#000
- = #500 >
- = #250 >
0
0 #000 2000 ,000 *000 5000 ?000
Wa/elength (nm+
6ig;re &1& The emission spectra o. a 3lac423ody radiator
many attempts to eplain it7 A particularly important theoretical study o. 3lac423ody radi2
ation 6as made around #$00 3y John William Strutt, the third Lord :ayleigh (#%*2 I
#$#$+ and James 9op6ood Jeans (#%-- I #$*?+7 At the heart o. this 6or4 lay the
concept that the radiation 6as emitted (or a3sor3ed+ 3y many QoscillatorsG 6hich
.ormed, or 6ere contained 6ithin, the structure o. the 3lac4 3ody7 According to
electromagnetic theory, electric charges oscillating 6ith .re0uency > emit radiation o.
the same .re0uency and .rom this the 6a/elength, <, o. the radiation can 3e readily
calculated since1
>< = c = /elocity o. light
!2.5.2"
9o6e/er, although the e0uation o3tained 3y :ayleigh and Jeans agreed 6ith eperi2
ment at long 6a/elengths it 6as completely at /ariance 6ith eperiment at short 6a/e2
lengths (Digure 272+7 At 6as especially distur3ing that the e0uation predicted that the
intensity o. the emitted radiation rises to inLnity as the 6a/elength approaches Kero7 This
impossi3le result 6as 4no6n as the ultra/iolet catastrophe7
&1)1% !lan#>s sol;tion to t$e ?la#>9?o/0 ra/iation pro?lem
Ca !lanc4 6as a man .or 6hom honour and success in his pro.essional li.e 6ere accom2
panied 3y great personal tragediesP he outli/ed his Lrst 6i.e and all .our o. their children7
9e 3elie/ed deeply that the only proper occupation .or a theoretician 6as attempting to
sol/e the most .undamental and challenging pro3lems o. the time7 At the end o. the #$th
century there 6as no more .undamental a pro3lem than that o. 3lac423ody radiation and in
#$0# !lanc4 had already 3een 6or4ing on it .or a3out si years7 Though he 6as 3y nature
a /ery conser/ati/e man, he .ound himsel. .orced to the conclusion that only an etremely
radical change in the ideas 6hich he and others had applied to the pro3lem hitherto could
lead to a relationship 3et6een =!<" and < 6hich 6ould agree 6ith eperiment in the
short26a/elength region7 9is re/olutionary idea 6as that1
An oscillator 0ith fre71ency > can %ossess only total energies, E
n
, 0hich satisfy the e71ation2
E
n
= nh> !n = 0 # 2 , . . ."
!2.5.,"
6here h is a uni/ersal constant, no6 4no6n as !lanc4Gs constant and n are the integers7
!lanc4 6as proposing that energy came in QpiecesG o. a certain siKe determined 3y the
.re0uency (>+7 Just as the atomic theory re0uires that matter is not inLnitely di/isi3le,
!lanc4Gs suggestion re0uires that the same is true o. energy7 When the possi3le energies o.
the oscillators 6ere restricted in this 6ay, !lanc4 o3tained a result in ecellent agreement
6ith the eperimental data o. Lummer and !ringsheim and a /alue .or h o. ?.55
#0
,*
J s7 !lanc4Gs e0uation may 3e epressed in the .orm1
=!<" d< =
or on a .re0uency scale as1
%( hc
<
5

!ep
%( h>
,
#
{hc, ;<-
#
d< !2.5.*a"
} #"
=!>" d> =
c
,

!ep {h>, ;-
d> !2.5.*3"
} #"
6here ; is BoltKmannGs constant and - the a3solute temperature7
2
2
The 3oldness o. !lanc4Gs hypothesis and the departure 6hich it represented .rom the
/ie6s accepted up to that time cannot 3e eaggerated7 The assumption that energy 6as
inLnitely di/isi3le into portions o. any siKe underlay all .ormulations o. classical mechan2
ics and 6as so .undamental to them that it 6as ne/er e/en stated7 ;o6 that assumption
had 3een sho6n 3y !lanc4 to 3e untena3le7 !lanc4 coined the term 71anta (singular
71ant1m + .or his little pac4ets o. energy (h>+ and systems 6hich can ha/e only certain
/alues o. energy, in this or an analogous manner, are said to 3e 71antised7 The num3er
n in '0uation (2757,+ 6hich gi/es the num3er o. 0uanta in the total energy !E
n
" is called
a 71ant1m n1m*er7
At is interesting to note that the e0uation proposed 3y !lanc4 .or the possi3le total
energies o. an oscillator, '0uation (2757,+, had to 3e modiLed 6hen the .ully de/eloped
0uantum theory o. the harmonic oscillator 3ecame a/aila3le a3out 25 years later7 At 6as
then sho6n that the correct .ormula .or E
n
is1
E
n
= !n +
#
"h> !n = 0 # 2 . . ."
!2.5.5"
and each energy le/el is seen to 3e raised 3y
#
h>, the Kero2point energy (see Chapter #0+7
This uni.orm discrepancy in the energy le/els caused no pro3lem in !lanc4Gs 6or4
and in early applications o. the de/eloping Qold 0uantum theoryG .or 6hich only energy
di..erences 6ere re0uired7 9o6e/er, pro3lems did arise 6hen attempts 6ere made to
eplain certain lo62temperature phenomena, such as the speciLc heats o. solids, and
these di.Lculties 6ere only o/ercome 6hen the .ully2Oedged 0uantum theory re/ealed the
presence o. the Kero2point energy7
&1)1& A @;alitatiAe interpretation o" t$e "orm o" t$e ?la#>9?o/0
emission #;rAe in t$e lig$t o" !lan#>s $0pot$esis
At is not immediately o3/ious that a change .rom a group o. classical oscillators ha/ing all
possi3le energies to a situation in 6hich the energies o. the oscillators are 0uantised can
ma4e such a dramatic di..erence to the predicted graph o. =(<+ /ersus <7 Since this is a
0uestion o. the energy o. the 0uantum and its dependence upon .re0uency, in Digure 27,
the !lanc4 .unction is plotted on a .re0uency rather than 6a/elength 3asis7 ;aturally,
since > is in/ersely proportional to <, the plot loo4s /ery di..erent in .orm though the
essential .eatures remain7 To interpret this .orm 6e Lrst note that in 3oth the classical and
0uantum /ie6 the num3er o. allo6ed .re0uencies in the .re0uency range 3et6een > and
> + d> N !>" d>, is gi/en 3y1
#
N !>" d> =
%(V >
2
d> !2.5.?"
c
,
6here V is the /olume o. the ca/ity7 The reason .or the restriction on the num3er o.
allo6ed .re0uencies 6ithin the ca/ity is that each .re0uency is associated 6ith a standing
6a/e 6hich must ha/e nodes at the ca/ity 6alls7 This re0uirement limits the possi3le
6a/elengths in @ust the same 6ay as the possi3le 6a/elengths o. a /iolin string are
limited7 'nergy no6 enters our discussion since the /alue o. =!>" d> is o3tained 3y
multiplying N !>" d> 3y, ?, the mean energy o. the oscillators7 Thus there 6ould appear
to 3e a strong tendency .or the graph o. =(>+ /ersus > to rise steeply 6ith increasing >7
But there is another .actor to 3e consideredP the 6ay in 6hich the a/aila3le energy is
0

#

'
n
e
r
g
y

d
e
n
s
i
t
y


#
0
#
-

(
J

m

,

9
K

#
+

Dre0uency (T9K+
#00070 %0070 ?0070 *0070 20070 070
50
*0
,0
20
- = ,?2075 >
;- = 570 #0
20
J
#0
'nergy in units o. ;-
0
#270 #070 %70 ?70 *70 270 070
;- VV hn
;- hn ;- WW hn
6ig;re &1' A 0ualitati/e interpretation o. the 3lac423ody emission spectrum
distri3uted o/er the oscillators and, again, classical and 0uantum theories do not di..er in
that 3oth use the BoltKmann distri3ution7 The ratio o. the num3ers o. oscillators (N
0
and
N
#
+ in t6o energy le/els (E
0
and E
#
+ is determined 3y the energy di..erence according
to the e0uation1
N
#
N
0
=

E E

ep
;-

E

ep !2.5.-"
;-
9o6e/er, the crucial di..erence 3et6een the classical and 0uantum /ie6s is re/ealed
6hen 6e determine the mean energy (?+ o. the oscillators7 Classically, 6ith a continuum
o. energy le/els, 6e Lnd1
6hilst the 0uantised energy2le/els gi/e1
? = ;- !2.5.%a"
h>
2.5.%3"
?
=
ep!h>, ;- " #
!
;oting that the eponential .unction may 3e epanded (see Appendi %+ as the series1
ep!h>, ;- " = # + h>, ;- + !h>, ;- "
2
,2U + !h>, ;- "
,
,,U
+
6e see that the 0uantum /alue o. ? tends to the classical /alue 6hen h> ;- and
6e ta4e @ust the Lrst t6o terms in the epansion7 Thus, at the lo62.re0uency end o.
the
2
2
graph (Digure 27,+, 6here there is e..ecti/ely a continuum o. energy le/els, the situation
is almost classical and the classical and 0uantum theory plots are /ery similar7 9o6e/er,
as 6e mo/e to higher .re0uencies the 0uantised spacing o. the energy le/els 3egins to
ma4e itsel. .elt7 A. 6e go immediately to the highest .re0uencies it is o3/ious that, at that
limit, the spacing 3et6een the energy le/els ( E = h>+ is so large that only the
lo6est
energy le/el is occupied7 A. all oscillators are in their lo6est energy state they cannot
emit and =(>+ must .all to Kero7 At .ollo6s, there.ore, that as 6e go .rom lo6 to high
.re0uencies a point is reached 6here the increasing energy2le/el spacing 3ecomes more
important than the increase in the energies o. the oscillators themsel/esP the graph o. =(>+
/ersus > goes through a maimum and 3egins its long .all to Kero7 'is3erg
#
has a /ery
good discussion o. the 3lac423ody pro3lem7
&1)1' Q;antisation in #lassi#al me#$ani#s
A 0uestion arises immediatelyP i. energy is 0uantised, 6hy 6as this not noticed 3e.ore
#$0#J Consider the /i3ration o. a macroscopic oscillatorP an idealised system consisting
o. t6o masses, each o. 07# 4g, @oined 3y a mass2less spring 6hich is #0 cm (07# m+
long at e0uili3rium and can 3e etended or compressedP (Digure 27*+7 A. the spring o3eys
9oo4eGs la6 in 3oth compression and etension then the potential energy, E, produced
3y a change o. length o. r is gi/en 3y1
E =
#
;! r "
2
so .or our particular spring1
E =
#
;!r 0.#0"
2
!Joules"
!2.5.$"
6here ; is the .orce constant measured in ; m
#
and r is the length to 6hich the spring
has 3een etended or compressed7 ; represents the sti..ness o. the spring and i. 6e
pull the masses apart to etend the spring and then release them the model /i3rates7
An our idealised system there 6ill 3e no losses o. energy and the /i3ration 6ill con2
tinue indeLnitely7 As the model /i3rates energy is continually echanged 3et6een 4inetic
and potential7 At the maimum and minimum spring lengths all the energy is poten2
tialP at the point 6hen the spring length is #0 cm all the energy is 4inetic7 The total
energy, potential plus 4inetic, is constant since energy must 3e conser/ed7 This is a suit2
a3le model .or an oscillating, homonuclear diatomic molecule, e7g7 hydrogen (9
2
+ or
oygen ("
2
+7
07# m
m = 07# 4g m = 07# 4g
; = #5 ; m
#
n = 27-? s
#
6ig;re &1( A macroscopic dum323ell oscillator
07000 07005 070#0 070#5 07020 07025 070,0
07000 #7%% -750 #?7%% ,0700 *?7%% ?-750
'
n
e
r
g
y


#
0
*

(
J
+
The potential energy .or a particular etension o. the spring, and hence the total
energy at any time, can 3e calculated .rom '0uation (2757$+7 The results o3tained using
a .orce constant o. #5 ; m
#
are sho6n in Ta3le 27#7 Since the energy is determined
3y !r 0.#0"
2
, the Lgures apply to 3oth etension and compression o. the spring
and they descri3e a para3ola (Digure 275+7 "scillations 6hich arise as a result o. a para3olic
potential energy cur/e are simple harmonic oscillations and the .re0uency o. oscillation
(>+ can 3e calculated 3y means o. the e0uation1
#
> =
2(


2;
!s
#
m
or 9K" !2.5.#0"
6here m is the mass o. each o. the t6o e0ual masses 6hich, in our case is #00 g = 0.#
4g7 We Lnd that the .re0uency is 27-5- 9K, i7e7 the model per.orms 27-5- oscillations
per second7
An this hypothetical model there is no limit on the potential energy 6hich 6e can
gi/e the systemP it simply depends upon the initial etension (or compression+ 6hich 6e
choose to impose upon the spring7 But note that although the energy may 3e di..erent,
the .re0uency o. oscillation is al6ays the same since it depends ('0uation 2757#0+ only
on m and ;7 But according to !lanc4 the energy is 0uantised in units o. h> = ?.?2?

#0
,*
2.-5- J = #.%2- #0
,,
J7 Comparing this result 6ith the Lgures in Ta3le
27#, 6e see that the 0uantum o. energy in this eample is a3out #0
2%
times smaller than
the energy o. the oscillator7 At is such a small 0uantity that there is no 6ay in 6hich 6e
could measure it or detect its presence 3y o3ser/ation o. the /i3rations o. our model7 As
.ar as our model is concerned, energy is e..ecti/ely continuous7
Ta?le &1% The energy o. the macroscopic model o. a diatomic oscillator as a .unction o. the
distance 3et6een the masses
(r 0.#+Hm
E,J
#0
*
%0
-0
?-750 X #0
*
J
?0
50
*?7%% X #0
*
J
*0
,0
20
Simple
harmonic
#0
oscillator
0
0705 0700 0705 07#0 07#5 0720 0725
<istance 3et6een masses (m+
6ig;re &1) The para3olic potential energy cur/e o. the macroscopic dum323ell oscillator
But i. 6e consider a molecule 6e shall Lnd that t6o .actors contri3ute to ma4e 0uan2
tisation a real o3ser/a3le phenomenon in a system o. atomic dimensions7 We ta4e as
our molecular model the hydrogen molecule (9
2
+7 'periment tells us that the mass o.
each atom in the molecule is #.?-,% #0
2-
4g and the .re0uency o. oscillation (>+
is
#.,#-5 #0
#*
9K7 :earranging '0uation (2757#0+ 6e
ha/e1
; = 2(
2
>
2
m
!2.5.##"
6hich, 6ith these data, gi/es a .orce constant o. 5-, ; m
#
7 And the 0uantum o. energy
.or the /i3rating hydrogen molecule is there.ore h> = %.-2? #0
20
J7 This is
much larger than that o. the macroscopic model 3ecause o. the great di..erence in the
/i3rational .re0uencies o. the t6o systems7
The 9I9 3ond length is -*7#- pm (# pm = #0
#2
m+ so, using '0uation (2757$+, a #0
Y etension o. the 3ond de/elops a potential energy o. !5-,,2" !-.*"
2
= #.5-
#0
20
J7 This Lgure is approimately one L.th o. the /alue o. h> .or the hydrogen
molecule cal2 culated a3o/e and 6e must there.ore epect that 0uantisation 6ill play
a much more important role in the /i3rational 3eha/iour o. the hydrogen molecule than it
does in the macroscopic model 6e discussed earlier7 Thus, 6e anticipate that the e..ects
o. 0uantisa2 tion 6ill 3e measura3le in atoms and molecules, 3ut not in macroscopic
systems7
An summary, 6e may say that it is the magnitude o. !lanc4Gs constant (h+ 6hich is the
determining .actor7 "nly 6hen energies are so small or .re0uencies so high that E h>
do the e..ects o. 0uantisation 3ecome /isi3le in our eperimental measurements7 Such
conditions are .ound 6hen 6e study the 3eha/iour o. atoms and molecules7
&1* THE !H2T2E5ECTRIC
E66ECT
!lanc4Gs solution o. the pro3lem o. the energy distri3ution o. 3lac423ody radiation 6as
etremely di.Lcult .or scientists to acceptP not least !lanc4 himsel. 6ho realised that,
i. it 6ere correct, it 6ould re0uire the recasting o. the 6hole o. classical physics7 The
thought that energy, li4e matter, 6as not inLnitely di/isi3le struc4 at the /ery .oundations
o. theoretical physics7 What 6as desperately needed 6as some conLrmation, some other
eperiment 6hich could 3e success.ully interpreted in terms o. a 0uantisation o. energy7
The 6orld o. physics 6aited until #$05 .or such e/idence, 6hich 'instein then pro/ided
6ith 3rilliant insight, though its true /alue 6as not recognised immediately7 The eperi2
mental o3ser/ation 6e shall discuss here is the %hotoelectric effect, 3ut in his #$05 paper
'insteinGs discussion ranged much more 6idely7
An #%%- 9ertK disco/ered that 6hen a 3eam o. ultra/iolet light .alls upon a metal
sur.ace particles capa3le o. conducting electricity are emitted .rom the metal7 An #$00
!hilipp 'duard Anton Lenard (#%?2 I #$*-+ pro/ed that the emitted particles 6ere
elec2 trons and .urther eperiments re/ealed the .ollo6ing salient .acts a3out the
photoelectric e..ect7
There is a threshold o. .re0uency (>
0
+7 Light ha/ing a .re0uency lo6er than >
0
does not e@ect electrons .rom the metal sur.ace, no matter 6hat the intensity o. the light7
But 6hen the .re0uency is increased a3o/e the threshold electrons appear
immediately7
The electrons e@ected 3y radiation o. .re0uency > greater than >
0
ha/e 4inetic energy
and this 4inetic energy increases as the .re0uency di..erence, > >
0
, increases7
The !hotoelectric '..ect 2#
A. the intensity o. the light is increased at a constant .re0uency the 4inetic energy o. the
e@ected electrons remains the same, 3ut they increase in num3er in direct proportion to
the intensity7
These eperimental o3ser/ations are completely at /ariance 6ith classical electromag2
netic 6a/e theory7 A. the energy o. light is spread out in a 6a/e a time delay 6ould 3e
epected, during 6hich the electron accumulates energy .rom the 6a/e, 3et6een the time
at 6hich the light source is s6itched on and the appearance o. the Lrst electrons7 The
delay 6as estimated theoretically to 3e a3out one minute 6hereas a delay o. approi2
mately #0
$
s 6as measured eperimentally7 Durther, since in classical theory energy is
accumulated .rom the light 6a/e, any light should 3e capa3le o. e@ecting electronsP the
process o. accumulation 6ould @ust ta4e longer .or less energetic light and there 6ould
3e no other dependence upon >7 Dinally, .or a gi/en period o. illumination, the 4inetic
energy o. the e@ected electrons is epected to increase 6ith the intensity o. the light, not
6ith its fre71ency7
'instein 3ased his #$05 interpretation o. the .acts o. the photoelectric e..ect on !lanc4Gs
hypothesis, reasoning as .ollo6s7 According to !lanc4, the oscillators in a light source
can only ha/e 0uantised energies gi/en 3y nh> (n = 0 # 2 , . . .+7 There.ore, as
the oscillators change their energies .rom nh> to (n #+h> and emit radiation o.
.re0uency > and energy h> then, at the moment o. emission, this radiation must emerge
as a pulse 6ithin a short period7 A. this pulse o. radiation then mo/es a6ay .rom the
source as a single entity rather than dispersing as a 6a/e, light may 3e considered to 3e a
stream o. pulses o. energy7 (We no6 call these pulses o. energy %hotons, though
'instein did not use that epressionP see Chapter %+7 A. the stream o. photons, each ha/ing
energy h>, .alls upon a metal sur.ace one o. t6o things may then occur7 A. the energy
(h>+ o. the photon is less than the 6or4 .unction (W +, 6hich is the energy re0uired to
e@ect an electron .rom the metal sur.ace, no photoelectron 6ill 3e o3ser/ed7 A. the photon
has more energy than that re0uired to e@ect the electron then the electron 6ill 3e e@ected
and, 3ecause energy must 3e conser/ed, the ecess o. energy 6ill 3e con/erted into the
4inetic energy (@E + o. the e@ected electron7 'instein there.ore proposed the .ollo6ing
e0uations .or the energetics o. the photoelectric e..ect1
h> = W + @E
(27?7#+ h>
0
= W
(27?72+ @E = h> h>
0
= h!> >
0
"
(27?7,+
These e0uations are in ecellent agreement 6ith the eperimental .acts as they are
4no6n today7 But it is not 6idely appreciated that, at the time o. 'insteinGs suggestion,
no 0uantitati/e eperimental data 6ere a/aila3le7 "nly the 0ualitati/e results outlined
a3o/e 6ere 4no6n to him and e/en these 6ere not uni/ersally accepted7 Thus, he 6as
not a3le to calculate a /alue o. !lanc4Gs constant 6ith his ne6 theory and his paper
actually contains /ery .e6 numerical results7 At is concerned solely 6ith descri3ing a
num3er o. eperimental o3ser/ations and interpreting them in terms o. a particle theory
rather than a 6a/e theory o. light7 The impact o. this ne6 hypothesis 6as not immediate,
3ut 6hen its signiLcance 6as recognised it 6on 'instein the #$2# ;o3el !riKe .or !hysics7
The lac4 o. high20uality eperimental data on 6hich to test it 6as an important .actor in
the slo6 appreciation o. 'insteinGs ne6 concept7 'le/en years 6ere to pass 3e.ore such
data 3ecame a/aila3le7
22 Drom Classical to &uantum Cechanics
Sodium
Lithium
:
e
t
a
r
d
i
n
g

p
o
t
e
n
t
i
a
l

(
8
+
&1*1% Einsteins t$eor0 o" t$e p$otoele#tri# e""e#t
#onBrme/ experimentall0
The eperimental 6or4 re0uired to clinch 'insteinGs hypothesis, at least as .ar as the
photoelectric e..ect is concerned, too4 many years to complete and turned out to 3e
etremely di.Lcult7 :o3ert Andre6s Cilli4an (#%?% I #$5,+, 6ho had earlier
achie/ed .ame .or his determination o. the charge on the electron, de/oted a3out ## years
to this pro3lem 3eginning in #$057 An #$#? he reported the deLniti/e summary o. his
6or4 on the photoelectric e..ectP his data .or lithium and sodium are illustrated in Digure
27?7
The horiKontal ais o. the Lgure gi/es the .re0uencies o. the lines o. the mercury
discharge lamp used to ecite the photoemission7 The /ertical ais records the minimum
/oltage re0uired to pre/ent the photoelectrons lea/ing the metal7 This is a measure o. the
4inetic energy o. the photoelectrons7 ;egati/e /alues o. the retarding /oltage indicate that
the electrons lac4ed su.Lcient energy to lea/e the metal sur.ace and had to 3e dra6n a6ay
.rom it7 'ach point is the result o. a series o. eperiments in 6hich the photocurrent .or
a range o. more negati/e /oltages is etrapolated 3ac4 to Kero current7 The slope o. the
graph o. retarding potential against .re0uency, 6hen con/erted to appropriate units, gi/es
the /alue o. h,e and, using the /alue o. e 6hich he himsel. had determined, Cilli4an .ound
/alues o. h = ?.5%* and ?.5?$ #0
,*
J s .rom his lithium and sodium data
respecti/ely7
A.ter a /ery care.ul consideration o. errors Cilli4an concluded that h = ?.5-
#0
,*
6ith an error o. 075 Y7 When he recalculated h using !lanc4Gs original
e0uation .or 3lac423ody radiation 6ith the most recent /alues o. the other physical
constants in/ol/ed,
Cilli4an .ound eactly the same /alue .or h 6ith an estimated error o. 07, Y7 This result
conLrmed 'insteinGs ideas in the most con/incing manner7 At is not surprising that this
3rilliant and eacting eperimental 6or4 6as also cited 3y the ;o3el Committee 6hen
they a6arded the #$2, ;o3el !riKe .or !hysics to Cilli4an, largely, 3ut not eclusi/ely,
.or his determination o. the charge on the electron7
#70
075
070
075
#70
#75
270
275
500 ?00 -00 %00 $00 #000 ##00 #200
Dre0uency (#0
#2
9K+
:eproduced 6ith permission .rom :7A7 Cilli4an, Phys. Rev7, +, ,55 (#$#?+7
The American !hysical Society7
6ig;re &1* Cilli4anGs data .or the photoelectric e..ect in lithium and sodium
We cannot lea/e this su3@ect 6ithout emphasising again @ust ho6 radical 'insteinGs
photon hypothesis 6as and ho6 small 6as the 0uantity o. hard eperimental e/idence
.or it at the time7 An the introduction to his paper, 6hich did more than anything else
to conLrm it, Cilli4an himsel. descri3ed 'insteinGs proposition as a Q. . . *old not to
say rec;less hy%othesis7GP 6ords 6hich 6ere 0uite @ustiLed in /ie6 o. the dominance o.
the 6a/e theory o. light in #$057 But, in spite o. its Oimsy eperimental 3ase and the
.act that 0uantitati/e eperimental conLrmation 6as such a long time coming, 'insteinGs
photon hypothesis 3rought a3out a complete change in our /ie6 o. light7 Throughout the
#%th and #$th centuries the 6a/e theory o. light had 3ecome increasingly dominant and
had etended into the description o. ne6ly disco/ered .orms o. electromagnetic radiation
such as ultra/iolet, in.rared and radio 6a/es7 'insteinGs interpretation o. the photoelectric
e..ect demanded a complete reappraisal o. the 6ay in 6hich light 6as regarded7 9e had
etended !lanc4Gs re/olutionary hypothesis 6hile introducing an e0ually radical concept
o. his o6n7
&1+ THE EMISSI2N S!ECTRA 26 AT2MS
". all the eperimental data 6hich classical theories appeared to Lnd di.Lcult to interpret,
the greatest 0uantity o. highly accurate data 6as contained in the photographs o. atomic
spectral emission7 A. a sample o. li4e atoms is heated to a su.Lciently high temperature,
*000

C say, the atoms a3sor3 energy .rom the .urnace and re2emit it in the .orm
o.
an atomic spectrum (Digure 27-+7 The spectrum consists o. a num3er, many hundreds in
some cases, o. /ery sharp lines o. precise 6a/elength (.re0uency+7 The lines loo4 li4e,
and indeed are, a 3ar code .or the atom and :o3ert Wilhelm Bunsen (#%## I #%$$+
and Gusta/ >irchho.. (6hose 6or4 on the 3lac423ody radiator has already 3een mentioned
in Section 275+ identiLed the pre/iously un4no6n elements caesium (a s4y23lue line
.ound in #%?0+ and ru3idium (a ru3y2red line .ound in #%?#+ 3y measuring the
spectra o. minerals heated to incandescence 3y BunsenGs .amous 3urner7 Later,
>irchho.. sho6ed that measurement o. the a3sorption o. light 3y atoms 6as similarly
characteristic7 Atomic emission and a3sorption spectra are among the most po6er.ul
0ualitati/e and 0uantitati/e analytical tools currently a/aila3le to us7
The lo6est spectrum is that o. copper and the one immediately a3o/e it is iron7 The remainder are the
spectra o. ore samples7 ZThe spectra are printed as [positi/es[ so that the emission lines appear 6hite on a
dar4 3ac4ground7\
6ig;re &1+ Some atomic emission spectra
]
]
Christian, Analytical Chemistry, 5th edn, :eprinted 6ith permission o. John Wiley & Sons, Anc7
But in the Lrst decade o. the 20th century the sharp lines o. the atomic spectrum
constituted a theoretical pro3lem o. great di.Lculty7 Throughout this decade eperimental
e/idence concerning the structure o. the atom 6as accumulating and in #$## 'rnest
:uther.ord (#%-# I #$,-+ proposed a model o. the atom in 6hich almost the 6hole
mass o. the atom 6as concentrated in a /ery small, positi/ely charged nucleus at the centre
6hile the negati/ely charged electrons occupied a much greater region o. space
surrounding the nucleus7 Since atomic spectra 6ere the result o. emission o. radiation 3y
atoms, it should ha/e 3een possi3le to dra6 conclusions a3out the structure o. atoms .rom
their detailed atomic spectra7 But there 6as a pro3lem7 Since the electrons 6ere negati/ely
charged and the nucleus positi/ely charged electrostatics predicted that the electrons
6ould 3e dra6n into the nucleus, destroying the atom immediately7 A 6ay in 6hich
such an e/ent might 3e pre/ented 6ould 3e i. the electrons 6ere to or3it the nucleus, li4e
planets around a sun, 6ith the .orce o. the electrostatic attraction 3et6een electron and
nucleus replacing the gra/itational attraction 3et6een planet and sun7 But e/en this 6as
no solution7 According to classical electromagnetic theory, a negati/e charge or3iting a
positi/e charge constitutes an oscillating dipole 6hich 6ould radiate energy, @ust li4e
9ertKGs spar4s (Section #7-+7 Thus the atom should continuously lose energy until the
electron .ell into the nucleus and the radiation emitted 6ould 3e o. continuously /arying
6a/elength (.re0uency+, not the sharp lines actually o3ser/ed7
&1+1% 8o$rs t$eor0 o" t$e str;#t;re o" t$e $0/rogen atom
The a3o/e 6as the dilemma 6hich .aced ;iels 9enri4 <a/id Bohr (#%%5 I #$?2+ in
#$#,7 9e attac4ed it 6ith that miture o. 3oldness and intuition 6hich had
characterised the 6or4 o. 'instein and proposed .our ne6 la6s7
Bohrs La!s of the $ydrogen %to& 'tructure
#7 The electron in the hydrogen atom or3its the nucleus in a circular path, li4e a planet
around the sun7
27 ". the inLnite num3er o. possi3le or3its, only those are allo6ed .or 6hich the or3ital
angular momentum o. the electron is an integral multiple o. !lanc4Gs constant di/ided
3y 2( 7
,7 Contrary to classical electromagnetic theory, electrons in these allo6ed or3its do not
radiate energy7
*7 When an electron changes its or3it a 0uantum o. energy (photon+ is emitted or a3sor3ed
in accordance 6ith the e0uation E = h>, 6here E is the di..erence in the
energy o. the t6o or3its7
An postulate 2 Bohr 6as .ollo6ing !lanc4Gs lead7 !lanc4 had proposed that the energies
o. the oscillators in a 3lac4 3ody could ha/e only certain 0uantised /aluesP Bohr 6as
suggesting a similar thing .or the electron or3its o. the hydrogen atom7 But instead o.
energy he chose to 0uantise the angular momentum o. the electron7 At is not easy to
say 6hy Bohr chose to 0uantise angular momentum rather than energy, 3ut it may 3e
that it 6as 3ecause the units o. !lanc4Gs constant (J s+ are the same as those o. angular
n = % ? 5 * ,
n
2
AHcm
#
%2 25%7$
AHcm
#
<(o3s7+Hnm <(calc7+Hnm
, $- *$27, #5 2,, ?5?75 ?5?75
* #02 %2,7% 20 5?5 *%?7, *%?7,
5 #05 2$#75 2, 0,, *,*72 *,*72
? #0? ?,272 2* ,-, *#07, *#07,
- #0- **07* 25 #%2 ,$-7# ,$-7#
% #0- $?570 25 -0? ,%$70 ,%$70
$ #0% ,2*7- 2? 0?? ,%,7? ,%,7?
#0 #0% 5%270 2? ,2, ,-$7$ ,-$7$
#0$ ?-%7% 2- *20 ,?*7- ,?*7-
n
2

(
n
2


*
+
Ta?le &1& The Lrst eight Balmer lines (2s n%P n = , * . . . #0+ o.
hydro2 gen BalmerGs .ormula1 <!calc7" = ,?*.-n
2
,!n
2
*"
state energy
]
]
Charlotte '7 Coore, Atomic Energy Levels, 8ol A, =S ;ational Bureau o. Standards,
Circular *?-, Washington <C, #$*$7
momentum7 9o6e/er, .ollo6ing the discussion o. Chapter #, it should 3e clear that, as
6ith the gas la6s o. Boyle and Gay2Lussac, there can 3e only one test o. BohrGs la6s
and that is 6hether they reproduce the eperimental Lndings7
Ta3le 272 lists the 6a/elengths o. a series o. emission lines o. the hydrogen atom
6hich, in #$#,, had 3een 4no6n .or many years7 They are called the Balmer lines 3ecause
Johann Ja4o3 Balmer (#%25 I #%$%+, a S6iss school teacher, had sho6n in #%%5 that
the
6a/elengths o. these lines (in nm = #0
$
m+ Ltted the simple
.ormula1
,?*.-n
2
< =
!n
2
*"
!n
=
, * 5 . . ." !2.-.#"
BalmerGs e0uation, 6hich predicts the 6a/elengths /ery accurately and 6as deduced
.rom the eperimental data alone, is illustrated 6ith a graph in Digure 27%7 Thus, the test
270
#75
#70
075
,50 *00 *50 500 550 ?00 ?50 -00
Wa/elength, l (nm+
6ig;re &1, A graph o. BalmerGs e0uation .or the hydrogen atom spectrum
0
0
0
=
o. BohrGs la6s is their a3ility to interpret '0uation (27-7#+7 The application o. the Bohr
model to BalmerGs e0uation is descri3ed in detail in Bo 27#7 An the net section the
results deri/ed there are used to test the Bohr theory against eperiment7
&1+1& Comparison o" 8o$rs mo/el wit$ experiment
As sho6n in Bo 27#, the Bohr model leads to '0uation (B27#7#,+ .or the 6a/elengths
o. the atomic spectral lines o. the hydrogen atom1
,2?
2
ch
,
<
e
*
m
e

n
2

n
2

*
!B2.#.#,"
"n e/aluating the .actor ,2?
2
ch
,
He
*
m
e
using the /alues .or the .undamental constants
listed in Appendi #, 6e o3tain1
,2?
2
ch
,
e
*
m
e
=
,2 !%.%5*#$"
2
2.$$-$2 !?.?2?0%"
,

#0
##%
!#.?02#%"
*
$.#0$,$ #0
#0-
=
,?*.50- #0
$
m
This is in ecellent agreement 6ith Balmer, i7e7 6ith eperiment, and conLrms the
/alidity o. BohrGs model .or the hydrogen atom spectrum7
&1+1' 6;rt$er /eAelopment o" 8o$rs t$eor0
The ecellent agreement o. BohrGs theoretical result 6ith the eperimental data em3odied
in BalmerGs e0uation 6as most grati.ying and, at the time, it mar4ed a /ery important step
.or6ard7 But la6 2, the ar3itrary imposition o. 0uantisation upon 6hat 6as essentially a
classical solution o. the pro3lem 6as to no oneGs li4ing, least o. all to BohrGs7 Durthermore,
strenuous e..orts 3y Bohr and others, nota3ly Arnold Johannes Wilhelm Sommer.eld
(#%?% I #$5#+, to apply a similar, semi2classical approach to atoms 6ith more than
one electron .ailed to gi/e results in agreement 6ith eperiment and it 6as clear that a .ully
accepta3le theory o. the structure o. the atom 6as yet to 3e .ound7 The search .or a
.orm o. mechanics applica3le to atoms and molecules 6as to last .or a .urther #2 years7
AmaKingly, 6hen a /ia3le theory 6as .ound, t6o apparently /ery di..erent theories 6ere
announced at almost the same time7 >arl Werner 9eisen3erg (#$0# I #$-5+
descri3ed his matrix mechanics in #$25 and 'r6in SchroM dinger (#%%- I #$?#+ his
0ave mechanics in #$2?7 But the t6o approaches 6ere soon sho6n to 3e di..erent
.ormulations o. the same theory (compare the ;e6tonian, Lagrangian and 9amiltonian
.orms o. classical mechanics+, and 6e shall deal only 6ith SchroM dingerGs /ersion here7
But 3e.ore 6e ta4e our Lnal step to 0uantum mechanics 6e must note a suggestion made
in his !h< thesis 3y de Broglie 6hich, though it 6as not su3stantiated 3y eperiment until
a.ter the ad/ent o. 0uantum mechanics, sho6ed /ery clearly that a pro.ound di..erence
6as to 3e epected 3et6een the description o. /ery small particles 3y classical and 3y
0uantum mechanics7 At also had a great inOuence on SchroM dinger 6ho, in his
.amous paper o. #$2?, descri3ed de BroglieGs thesis as QinspiredG7
&1, /e 8R25IES !R2!2SA5
Louis 8ictor !ierre :aymond !rince de Broglie (#%$2 I #$%-+ descended .rom a
no3le .amily 6ho had ser/ed many Drench 4ings7 9e studied history 3e.ore ta4ing up
physics and in his doctoral dissertation (#$2*+ he reasoned as .ollo6s1
de BroglieGs !roposal 2-
According to 'insteinGs theory o. relati/ity1
E = mc
2
!2.%.#"
3ut 'instein, .ollo6ing !lanc4, also suggested that1
E = h> = hc,< !2.%.2"
there.ore, i. the momentum (%+ o. the photon as a particle is mc, then1
% = mc = E,c = h,<
!2.%.,"
and i. this result applies to other particles as 6ell as to photons, then all mo/ing particles
should 3e associated 6ith a 6a/elength (<+ gi/en 3y the e0uation1
< = h,% = h,mv
!2.%.*"
6here m and v are the mass and /elocity o. the particle respecti/ely7
This remar4a3le suggestion 6as conLrmed .or electrons 3y Clinton Joseph <a/isson
(#%%# I #$5%+ and Lester 9al3ert Germer (#%$? I #$-#+ 6ho, in #$2-, demonstrated
that a 3eam o. electrons directed at the sur.ace o. a nic4el crystal 6ere selecti/ely
di..racted at certain angles, @ust as F2rays are di..racted, 3y the regularly spaced layers
o. atoms in a crystal7
A similar eperiment 6as per.ormed independently 3y George !aget Thomson (#%$2 I
#$-5+ in #$2-7 An ThomsonGs eperiment, electrons 6ere accelerated 3y potentials o.
3et6een #0 and ?0 48 as a result o. 6hich, i. de Broglie is correct, their associated
6a/elengths 6ould lie 3et6een #2 and 5 pm respecti/ely7 This 6a/elength range is some
20 to 50 times smaller than the spacing 3et6een atoms in a metal and Thomson Lred a
/ery narro6 3eam o. his accelerated electrons through etremely thin (#0
-
m+ .oils o.
gold and platinum7 9e placed a photographic plate on the .ar side o. the .oil and 6hen
he de/eloped the plate .ound it to sho6 the circular inter.erence pattern 6ell 4no6n
.rom the corresponding eperiments 6ith light 3eams7 Durthermore, measurement o. the
inter.erence pattern and a 4no6ledge o. the /elocity o. the electrons and the spacing o.
the atoms in the metal .oil pro/ided a 0uantitati/e proo. o. de BroglieGs e0uation7 Cany
su3se0uent eperiments 6ith hea/ier particles ha/e conLrmed the early results7
]
The deep signiLcance o. this result is apparent 6hen 6e consider a simpliLed /ersion
o. ThomsonGs eperiment (Digure 27$+ in 6hich a 3eam o. electrons is directed at a screen
containing @ust t6o slits 6ith a photographic plate to o3ser/e the results7 Drom eperiment
6e 4no6 that an inter.erence pattern is o3ser/ed on the plate only i. there are t6o (or
more+ slits in the screen7 With one slit no inter.erence pattern is seen7 Also, 6e can
reduce the intensity o. the electron 3eam to such a le/el that 6e may consider the Lnal
pattern on the plate to 3e the accumulation o. the results o. many eperiments, each 6ith
an indi/idual electron7 But ho6 can this 3e interpreted i. the electron is a particleJ A
particle can only pass through one o. the slits, 3ut the eperiment seems to imply that the
presence o. a .urther slit, through 6hich the electron did not pass, has had an inOuence
on the electronGs tra@ectoryU
We are on /ery treacherous ground here7 'perience has sho6n that 6e cannot spea4
o. the path o. a particle in 0uantum mechanics in the same 6ay as 6e do in classical
mechanics7 We can only spea4 o. those things 6hich 6e can o3ser/e7 An this case 6e can
]
A nice anecdote is told a3out the Thomsons7 The .ather (JJT+ 6on the ;o3el !riKe .or !hysics in #$0? .or sho6ing that the
electron 6as a particle7 The son (G!T+ 6on the same priKe in #$,- .or sho6ing that the electron 6as a 6a/eU
2% Drom Classical to &uantum Cechanics
'lectron source 'lectron source 'lectron source
!hotographic plate !hotographic plate !hotographic plate
A single open slit
produces one 3and
on the photo2plate
A single open slit
produces one 3and
on the photo2plate
When 3oth slits are open
an inter.erence pattern o.
many 3ands is produced
6ig;re &1- An idealised representation o. G7!7 ThomsonGs eperiment
see the spot produced on the photographic plate 3y the electron, 3ut 6e cannot o3ser/e the
QpathG 6hich it has ta4en 3et6een the electron source and the plate and 6e must not ma4e
in.erences a3out 6hat that path might, or might not, ha/e 3een7 A much more detailed
discussion o. this pro3lem has 3een gi/en 3y Deynman
2
and 6e shall return to the su3@ect
o. 6hat 6e can and cannot 4no6 in Chapter ,7 At the moment 6e must continue on our
di.Lcult 3ut 6ell2deLned path Q.rom classical to 0uantum mechanicsG, .or 6e ha/e almost
reached our @ourneyGs end7
&1- THE SCHR2
C
3INER EQUATI2N
The title o. the paper in 6hich SchroM dinger announced his ne6 mechanics 6as
Q31anti+ Bation as an Eigenval1e Pro*lem G and in the Lrst paragraph he 6rote1
Q:n this comm1nication : 0ish to sho0 Crst for the sim%lest case of the non+relativistic and 1n%er+
t1r*ed hydrogen atom that the 1s1al r1les of 71antisation can *e re%laced *y another %ost1late in
0hich there occ1rs no mention of 0hole n1m*ers. :nstead the introd1ction of integers arises in the
same nat1ral 0ay as for exam%le in a vi*rating string for 0hich the n1m*er of nodes is integral.
-he ne0 conce%tion can *e generalised and : *elieve that it %enetrates dee%ly into the tr1e nat1re
of the 71ant1m r1les7
]
The title chosen .or his paper 3y SchroM dinger is /ery signiLcant, and 6e shall
return to it later7 But let us Lrst eamine the opening paragraph 0uoted a3o/e7
SchroM dinger immediately ma4es clear that he is going to deal only 6ith the simple case o.
the hydrogen atom7 9e is not going to include the e..ects o. the theory o. relati/ity in his
discussion, nor 6ill the atom 3e distur3ed (pertur3ed+ 3y any eternal .orces7 The second
hal. o. the Lrst sentence sho6s that it is the ar3itrary imposition o. 0uantisation 6hich is
SchroM dingerGs
]
A ha/e ta4en this 0uotation, ver*atim, .rom Linus !auling and '7 Bright WilsonGs Q:ntrod1ction to 31ant1m 5echanics G,
pu3lished in #$,57
*
Li4e the 3oo4 itsel., the translation o. the original German can scarcely 3e impro/ed upon7
The SchroM dinger '0uation 2$
target and the second sentence re/eals that he has .ound a theory in 6hich 0uantisation
arises naturally7
To illustrate the 6ay in 6hich integers can arise naturally in theoretical models o. phys2
ical phenomena, SchroM dinger re.ers to the /i3ration o. a stretched string, 6hich can
only /i3rate in such a 6ay as to produce the .undamental .re0uency and the Lrst, second,
third,
. . . nth . . . o/ertone, or harmonic, and .or 6hich the string has 0 # 2 , . . . n . . .
nodes
respecti/ely 3et6een the Led points at its ends7 9ere 6e must 3e6are7 SchroM
dingerGs .orm o. the ne6 mechanics has 3ecome 4no6n as 6a/e mechanics and he is here
illustrat2 ing his ne6 results 6ith the 6ell24no6n properties o. 6a/es on stretched strings7
But this does not mean that his e0uation can 3e deri/ed .rom such considerations7 The
SchroM dinger e0uation is not deri/a3le .rom classical mechanics, it is a ne6 postulate
as he himsel. ma4es clear in the 0uotation a3o/e7 So, 6hat is this ne6 postulateJ The
0uestion ta4es us 3ac4 to consider the title o. SchroM dingerGs paper7
&1-1% Eigen";n#tions an/ eigenAal;es
German is a language 6ith a remar4a3le a3ility .or 3uilding compound 6ords such as
Eigenf1n;tion and Eigen0ert7
,
At is easy to translate the second parts o. the a3o/e German
6ords Q91n;tion G = Qf1nction G and QWert G = Qval1eG (German nouns al6ays 3egin
6ith an upper2case letter+, 3ut it is /ery di.Lcult to Lnd a suita3le translation .or the
0uali.ying 6ord QEigen G7 The 6ord QspecialG has occasionally 3een used, 3ut it does
not imply an aspect o. Q3elonging toG 6hich QEigenG also has7 Thus, an eigen/alue is not
only a special /alue it also 3elongs to something, to its o6n special .unction and an
operator in .act (see Bo 272+7 The situation is 3est illustrated 6ith an eample o. an
eigen/alue2eigen.unction e0uation1
D
2
D
D
2
!sin ," =
D
!, cos ," = $ sin ,
This e0uation is a rather unusual one7 The mathematical operator, D
2
,D
2
, operates
on the .unction sin(, + (6e sho6 it in t6o steps to ma4e the process clear+ to gi/e
eactly the same .unction 3ac4 again, 3ut multiplied 3y a num3er, $ in this case7
There are rather .e6 cases 6here an operator, e7g7 +, , , , integrate, di..erentiate,
6hen applied to a .unction gi/es the .unction 3ac4 again multiplied only 3y a num3er7
When this unusual situation does occur the .unction is 4no6n as an eigen.unction o. the
operator and the num3er as the associated eigen/alue7 At is this mathematical phenomenon
6hich lies at the heart o. SchroM dingerGs mechanics7 9e disco/ered a 6ay o.
.ormulating an operator .or the energy o. the electron in the hydrogen atom and then
determined the eigen.unctions and eigen/alues o. that operator7 The eigen/alues are
then the possi3le energies o. the electron in the hydrogen atom, as could 3e tested
immediately 3y a comparison 6ith the eperimental spectral data7 The eigen.unctions are
.unctions 6hich descri3e the possi3le 6ays in 6hich the electron may 3e distri3uted
around the nucleus o. the hydrogen atom, each distri3ution 3eing associated 6ith a
particular energy gi/en 3y the associated eigen/alue7 These hydrogenic eigen/alues and
eigen.unctions 6ill 3e discussed in detail in Chapter 57 At the moment 6e shall Lnd it
easier i. 6e Lrst consider the eigen/alues and eigen.unctions o. some e/en simpler
pro3lems (Chapter ,+7 But simple though they are, 6e shall Lnd that these pro3lems ha/e
solutions 6ith important chemical applications7
,0 Drom Classical to &uantum Cechanics
&1%. 8I85I2RA!HY AN3 6URTHER REA3IN
#7 :7C7 'is3erg, 91ndamentals of 5odern Physics, Wiley, ;e6 Ror4, #$?-7
27 :7 Deynman, Six Easy Pieces, !enguin Boo4s, London, #$$%7
,7 An eample .re0uently 0uoted is1 Eona1dam%fschiffartsgesellschafts;a%it aF nsfra1 = the
6i.e
(fra1 + o. a captain (;a%itaF ns + in the <anu3e (Eona1 + steam2ship (dam%fschiffarts +
company
(gesellschaft +7
*7 L7 !auling and '7B7 Wilson, :ntrod1ction to 31ant1m 5echanics, CcGra629ill, ;e6 Ror4,
#$,57
82D &1% 8o$rs mo/el o" t$e $0/rogen atom in /etail
Motion in a #ir#le
BohrGs model o. the hydrogen atom pictures the electron or3iting the nucleus li4e a
planet around the sun7 The theory appeals to the results o. the classical mechanics o.
motion in a circle so it 6ill 3e use.ul i. 6e deri/e those 6e re0uire 3e.ore 6e start7
Digure B27#7#(a+ sho6s a mass m mo/ing 6ith a constant speed (v+ along a circular
path o. radius r centered at "7 Though the speed is constant, the /elocity, 6hich
is a /ector 0uantity and there.ore has direction as 6ell as magnitude, is not7 The
magnitude o. the /elocity o. the mass is its speed, 6hich is constant, 3ut its direction
is continuously changing7 The /elocity /ector (v+ is al6ays at right angles to the
radial /ector (r+ and Digure B27#7#(3+ illustrates the situation at t6o closely spaced
instants in time during 6hich the mass has mo/ed through a /ery small angle !d^"7
The distance mo/ed along the arc, ds, is e0ual to r _ /E i. /E is measured in radians7
Also, the speed along the arc is v = ds,dt 7 An Digure (c+ the di..erence in the
t6o
/elocity /ectors, dv = v
2
v
#
, is .ound 3y means o. /ector su3traction7 Since
the magnitudes o. v
2
and v
#
are e0ual to the constant v, .or small angles 6here the
arc
o. the circle and its chord are not apprecia3ly di..erent in length, dv = v _ /E7
Thus
6e ha/e1
ds = r _ /E and dv = v _ /E
'liminating /E gi/es1 dv,ds = v,r 7
The acceleration, a, o. the mass can no6 3e .ound 3ecause1
dv ds dv
v v
2
a =
dt
=
dt

ds
= v _
r
=
(B27#7#+
r
2
2
#
#
ds
r r
r
/E
r
"
2
/E d

#
(a+
6ig;re 8&1%1% Cotion in a circle
Boes .or Chapter 2 ,#
ds = r /E
d =
2
I
#
=


/
E
(3+
(c+
At is clear .rom Lgure (c+ that .or /ery small angles !/E", the change in /elocity
!dv" is at right angles to v and there.ore directed along r to6ards "7 Thus, i. the
change in /elocity is directed to6ards " so also must 3e the acceleration7
The angular momentum (l+ generated 3y the counter2cloc46ise motion illustrated
in (a+ is gi/en 3y the /ector product1
l = r p = r mv = rmv
(B27#72+ The last e0uality .ollo6s 3ecause r and v are al6ays at right angles to
each other
and the /ector product o. t6o /ectors is the product o. their magnitudes multiplied 3y
the sine o. the angle 3et6een them7 The direction o. the /ector l is out o. the paper
to6ards the reader7
Ang;lar moment;m an/ energ0
Dor the system descri3ed a3o/e all energy is 4inetic energy 6hich can 3e readily
epressed in terms o. the angular momentum1
mv
2
!mv"
2
!l,r "
2
l
2
E!4inetic energy" =
2
=
2m
=
2m
=
2mr
2
(B27#7,+
T$e 8o$r mo/el
Consider an electron o. mass m
e
and charge e mo/ing 6ith /elocity v in a circular
or3it o. radius r around a much hea/ier nucleus o. charge +e (Digure B27#72+7 The
electron .ollo6s this path 3ecause o. the coulom3ic .orce o. attraction, e
2
,*( ?
0
r
2
, pulling it to6ards the nucleus7 ?
0
is the /acuum permitti/ity7 The electron does
not .all into the nucleus 3ecause o. its /elocity at right2angles to the line 3et6een the
t6o particles, the radial /ector7 But, as sho6n a3o/e, the coulom3ic .orce does
cause an
acceleration o. the electron to6ards the nucleus e0ual to v
2
,r , 6here the negati/e
e
m
e
5 r
)e
6ig;re 8&1%1& BohrGs model o. the hydrogen atom
o
e
=
o
o o
o
e

#
sign indicates that the acceleration, li4e the .orce 6hich causes it, is in the direction
o. decreasing r 7 ;o6, according to ;e6ton, .orce = mass acceleration so1
e
2
*( ?
o
r
2
=
m
e
v
2
r
or r =
e
2
*( ?
o
m
e
v
2
(B27#7*+
The discussion up to this point has 3een 3ased entirely upon classical theory and
there.ore 6e Lnd that no restriction is placed upon the radius o. the electronGs or3it
(r +7 Dor any choice o. r a /elocity can 3e .ound to 3alance the a3o/e e0uation7 BohrGs
second la6 introduces 0uantisation 6ith the postulate that only those or3its .or 6hich
the or3ital angular momentum is an integer multiple o. h,2( are allo6ed7 The angular
momentum is m
e
vr so BohrGs 0uantum condition is1
m
e
vr = nh,2( n = # 2 , . . .
(B27#75+
n = Kero is not permitted 3ecause it 6ould imply either v = 0, gi/ing rise to an
inLnite radius ('0uation (B2727#++ or r = 07 A. the allo6ed or3its satis.y '0uation
(B27#75+ then the allo6ed /alues o. the radius can 3e o3tained 3y using '0uation
(B27#75+ to eliminate v .rom '0uation (B27#7*+ gi/ing1
e
2
r =
*(? m
*(
2
m
2
r
2
e
or m r
n
2
h
2
?
o
n
2
h
2
(B27#7?+
e
2
(
and using '0uation (B27#75+ again1
nh nh
e
2
( e
2
v =
2(m r
=
2(

? n
2
h
2
=
2? nh
(B27#7-+
e o o
To o3tain the total energy, E, o. the atom 6e use1
E = potential energy + 4inetic energy
so that1
e
2
E =
*(? r
+
m
e
v
2
2
2
e
2

e
2
( m
e

m
e

e
2
(B27#7%+
=
*( ?
o
e
*
m
e
?
o
n
2
h
2
+

#

2 2?
o
nh
e
*
m
e
=
*?
2
n
2
h
2
# +
2
=
%?
2
n
2
h
2
The presence o. the 0uantum num3er n on the right2hand side o. '0uation (B27#7%+
.or E sho6s 6hy n cannot 3e Kero and that 6e ha/e 0uantisation o. the total energy
o. the hydrogen atom7 We recognise this 3y 6riting the 0uantum num3er in 3rac4ets1
E!n" =


e
*
m
e

(B27#7$+
n
2
%?
2
h
2
We no6 re0uire to see i. 6e can reproduce BalmerGs '0uation ('0uation (27-7#++7
According to BohrGs .ourth postulate, the energy o. a spectral line is gi/en 3y the
0
2 #
=
di..erence 3et6een t6o o. the a3o/e 0uantised energy /alues o. the hydrogen atom,
i7e7 the energy calculated .or t6o di..erent 0uantum num3ers, n
#
and n
2
say7 Thus1
e
*
m
e

# #

e
*
m
e
!n
2
n
2
"
E!n
2
" E!n
#
" = E =
%?
2 2 2
=
o
n h n
2
n
2
%?
2
n
2
h
2
n
2
n
2
# 2 o # 2
(B27#7#0+
But the .re0uency o. light (>+ and the 6a/elength (<+ are related 3y the /elocity
(c+ in the e0uation c = ><, so that1
E = h> = hc,<
(B27#7##+ There.ore, the 6a/elength o. a line in the Balmer series is1
%?
2
ch
,
n
2
n
2
%n
2
?
2
ch
,

n
2
< =
0

# 2 # 0
=
2
(B27#7#2+
e
*
m
e
n
2
n
2
e
*
m
e

n
2
n
2
2 # 2 #
A comparison o. this e0uation 6ith '0uation 27-7# suggests that n
#
= 2 and n
2
=
n, and i. 6e ma4e these su3stitutions our epression .or < can no6 3e 6ritten1
,2?
2
ch
,
<
e
*
m
e

n
2

n
2

*
(B27#7#,+
The crucial test o. BohrGs la6s is no6 o3tained 3y e/aluating the .actor ,2?
0
2
ch
,
, e
*
m
e
in '0uation (B2727#,+7 This calculation is carried out in Section 27-727
6here ecellent agreement 6ith Balmer, and there.ore 6ith eperiment is .ound7
82D &1& 2perators
We can di/ide the sym3ols used in mathematics into t6o types, the o%erators and the
o%erands7 The operands are the num3ers, or in the case o. alge3ra, the letters 6hich
represent the num3ers7 The operators are the sym3ols 6hich tell us 6hat 6e ha/e
to do 6ith the num3ers7 Thus, in the epression 2 + 5, the operator, +, tells us that
6e are to add the num3er 5 to the num3er 27 Similarly, 2 5 indicates that 5 is
to 3e multiplied 3y 27 The operator

tells us to ta4e the s0uare root o. the
operand7
As eamples o. more complicated operators 6e may ta4e those .or di..erentiation
and integration 6hich, as it happens, occur .re0uently in 0uantum mechanics7 An a
crude analogy 6e might say that the surgeon is the operator and the patient the
operand7
!airs o. operators are lin4ed 3y a /ery important property 6hich is independent
o. the operand7 This may 3e illustrated using the operators .or multiplication 3y y,
y, multiplication 3y K, K, and ta4ing the s0uare root,

7 As the operand 6e
shall
use *y
,
7
Dirst 6e ta4e the operators y and K and apply them to the operand in the
order y K7 We o3tain1
y !K Z*y
,
\" = y !*Ky
,
" = *Ky
*
And i. 6e apply the t6o operators in the re/erse order 6e get the same result, i7e71
K !y Z*y
,
\" = K !*y
*
" = *Ky
*
But i. 6e choose the operator pair y and

, 6e Lnd that the order in 6hich 6e


apply them is important 3ecause1
# ,
But1
!K Z*y
,
\"
=
!*Ky
,
" = 2K
2
y
2
, ,
K Z*y
,
\ = K !2y
2
" = 2Ky
2
We say that the operator pair y and K comm1te, 3ut the pair y and

do
not
commute7 The commutation or non2commutation o. pairs o. operators plays a /ery
important role in 0uantum mechanics as 6e shall see in Chapter ,7
!R285EMS 62R CHA!TER &
#7 Dor the special case o. a planet 6ith a circular or3it, deduce >eplerGs third la6 .rom
;e6tonGs la6s7
27 Calculate the radius o. the circular or3it o. a geostationary satellite, i7e7 a satellite
6hich remains in eactly the same position a3o/e the sur.ace o. the earth7 <etermine
!ro3lems .or Chapter 2 ,5
its altitude and or3ital /elocity7 Assume that the mass o. the earth is 5.$%, #0
2*
4g,
its radius is ?.,-% #0
?
m and the gra/itational constant G = ?.?-, #0
##
m
,
4g
#
s
2
7
,7 'stimate the 6or4 .unctions W(;a+ and W(Li+ .rom Digure 2757
*7 The most po6er.ul tennis players are reputed to ser/e the 3all at a speed o. a3out
200 4mHhour7 A. the mass o. the 3all is 5% g calculate its 6a/elength7
57 ConLrm the range o. 6a/elengths 0uoted in Section 27% .or ThomsonGs accelerated
electrons7
?7 By epanding the eponential in '0uation 2757*3, sho6 that =!>" >
2
6hen h> ;- 7
Chapter ,
T$e Appli#ation o" Q;ant;m
Me#$ani#s
,70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,%
,7# "3ser/a3les, operators, eigen.unctions and eigen/alues . . . . . . . . . . . . . . ,%
,72 The SchroM dinger method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$
,7, An electron on a ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *0
,7,7# The 9amiltonian operator .or the electron on a ring . . . . . . . . . . *0
,7,72 Solution o. the SchroM dinger e0uation . . . . . . . . . . . . . . . . . . . . *#
,7,7, The accepta3le eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . *#
,7* 9uM c4elGs (*N + 2+ rule1 aromaticity . . . . . . . . . . . . . . . . . . . . . . . . . . **
,75 ;ormalisation and orthogonality (Bo ,72+ . . . . . . . . . . . . . . . . . . . . . . *?
,7? An electron in a linear 3o . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *?
,7?7# The 9amiltonian operator .or an electron in a linear 3o . . . . . . . *?
,7?72 The accepta3le eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . *-
,7?7, Boundary conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *%
,7- The linear and angular momenta o. electrons conLned 6ithin a
one2dimensional 3o or on a ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . *%
,7-7# The linear momentum o. an electron in a 3o . . . . . . . . . . . . . . *$
,7-72 The angular momentum o. an electron on a ring . . . . . . . . . . . . 50
,7% The eigen.unctions o. di..erent operators . . . . . . . . . . . . . . . . . . . . . . . 52
,7$ 'igen.unctions, eigen/alues and eperimental measurements . . . . . . . . . . 5,
,7#0 Core a3out measurement1 the 9eisen3erg uncertainty principle . . . . . . . . 55
,7## The commutation o. operators (Boes 272 and ,7?+ . . . . . . . . . . . . . . . . 5-
,7#2 Com3inations o. eigen.unctions and the superposition o. states . . . . . . . . 5%
,7#, "perators and their .ormulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,7# !osition or co2ordinate, x . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,72 !otential energy, V

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,7, Linear momentum, p

x
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#,7* >inetic energy, W

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#,75 Angular momentum, L

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#* Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#5 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?#
!ro3lems .or Chapter , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -#
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
,% The Application o. &uantum Cechanics
2
'1. INTR23UCTI2N
Consider the hydrogen molecule, 9I97 The hydrogen atoms each ha/e a mass o. #.?-*
#0

2-
4g and their nuclei are separated 3y a 3ond o. length

-*

#0

#2
m7 An actual
.act, this is the e0uili3rium 3ond length o. the molecule, .or this minute entity is in
constant /i3ration 6ith a .re0uency o. #,2 #0
#2
oscillations per second7 Just pause .or
a moment and try to picture the molecule7 An the time it ta4es to 3lin4, .or eample, it 6ill
ha/e completed #,2 million, million /i3rations7 As it permissi3le to descri3e such a motion
as a Q/i3rationG 6hen 6e cannot really e/en imagine such .re0uenciesJ Casses as small as
#0

2-
4g and distances as short as #0

#2
m are indescri3a3ly remote .rom the phenomena
6hich 6e eperience directly 6ith our o6n senses7 &uantum mechanics, 6hich has no6
stood the test o. more than -5 years o. rigorous application, is the mathematical model
6hich has 3een constructed to descri3e atomic and molecular systems and to interpret the
results o. the eperiments 6hich 6e per.orm upon them7 But it should come as no surprise
6hen the picture o. this 6orld o. atoms and molecules, dra6n 3y 0uantum2mechanical
methods, sometimes seems /ery strange to us7
The early pioneers o. the su3@ect soon disco/ered that, in order to 4eep on course in
interpreting o. the results o. 0uantum mechanics, 6e must 3e /ery care.ul to .ocus our
attention upon the 0uantities 6hich can 3e measured in a particular eperimental system
and re.rain .rom speculation a3out those things 6hich cannot7 (:ecall the inter.erence
o. photons discussed in Section 27%7+ Thus, to return to the eample o. the hydrogen
molecule, the e0uili3rium 3ond length o. the molecule can 3e 3oth measured and cal2
culated to high degrees o. accuracy7 But there is no 6ay in 6hich the paths o. the t6o
electrons 6hich .orm that 3ond can 3e .ollo6ed or descri3ed7 We can only gi/e a Lgure
.or the pro3a3ility o. Lnding an electron (6e cannot say 6hich oneU+ at any particular
point in space7
Thus, in this chapter 6e are concerned not only to illustrate the 6ay in 6hich 0uantum
mechanics is applied, 3ut also to ma4e clear @ust 6hat in.ormation can 3e o3tained .rom
0uantum2mechanical calculations or 3y eperiment7 We shall Lnd that, though the in.or2
mation 6hich 6e can o3tain is restricted 6hen compared 6ith that a/aila3le in classical
mechanics, this is not so surprising 6hen 6e consider the .undamental limitations 6hich
must apply to measurements on atomic and molecular systems7
'1% 28SERVA85ES< 2!ERAT2RS< EIEN6UNCTI2NS
AN3 EIENVA5UES
Any phenomenon 6e can o3ser/e, and particularly one 6hich 6e can measure and assign
a numerical /alue to, e7g7 energy or angular momentum, is 4no6n as an o*serva*le7 At
is the primary o3@ecti/e o. 0uantum mechanics to pro/ide a theory 3y means o. 6hich
the /alues o. such o3ser/a3les can 3e calculated7 Just as classical mechanics pro/ides an
e0uation .or determining the 4inetic energy o. a mo/ing mass (47e7
=
#
mv
2
+, so 0uantum
mechanics pro/ides us 6ith an e0uation 3y means o. 6hich the 4inetic energy o. a mo/ing
electron can 3e determined7
An Section 27$ 6e sa6 that, 6hen proposing his ne6 6a/e mechanics, 'r6in SchroM
2 dinger suggested that the mathematical concept o. eigen.unctions and eigen/alues
6ould 3e .ound to lie at the heart o. any theory in 6hich 0uantisation arose naturally,
rather
The SchroM dinger Cethod ,$
than 3eing ar3itrarily imposed7 All su3se0uent 6or4 has demonstrated that SchroM
dingerGs intuition 6as indeed correct and in the application o. 0uantum mechanics
today 6e .ormulate SchroM dingerGs method in terms o. .our entities1 an o*serva*le,
the particu2 lar 0uantum2mechanical o%erator associated 6ith that o3ser/a3le and the
eigenf1nctions and eigenval1es o. that operator7 The operator, eigen.unction and
eigen/alue are related in the e0uation1
4%erator operating on Eigenf1nction = Eigenval1e Eigenf1nction !,.#.#"
The usual mathematical .ormulation o. the relationship is1
:


n
= r
n

n
!,.#.2"
and a speciLc eample is1 D
2
!sin ax",D x
2
= a
2
sin ax7 The operator,
:

(designated as
such 6ith the caret mar4 or circumOeP D
2
,D x
2
in the eample+, operates upon the
eigen2
.unction,
n
(sin ax+, 6hich is a .unction o. the co2ordinate system in 6hich 6e place the
atom or molecule 6e are studying, e7g7 the Cartesian co2ordinates x y and B7 The result is
the eigen.unction multiplied 3y the eigen/alue, r
n
(

a
2
+7 We shall see 3elo6 that the .act
that the eigen.unction is descri3ing a real atomic or molecular system places important
limitations upon the .orm 6hich it may ta4e7 The o3ser/a3le appears in '0uations (,7#7#+
and (,7#72+ as the eigen/alue, r
n
, 6hich is simply a num3er that is the /alue o. the o3ser/2
a3le in the units 6e ha/e chosen .or the calculation, e7g7 an energy in J7 The su3script,
QnG, indicates that there are generally many eigen.unctions o.
:

and an e0ual num3er o.


corresponding eigen/alues, each characterised 3y a di..erent /alue o. n7 We shall Lnd that
n is a 0uantum num3er, or more o.ten a set o. 0uantum num3ers, e7g7 those descri3ing
the electronic state o. an atom7
'1& THE SCHR2
C
3INER METH23
SchroM dingerGs method consists o. three 3asic
steps1
#7 <etermine the operator associated 6ith the o3ser/a3le to 3e calculated7
27 Dind the eigen/alues and eigen.unctions o. the operator7
,7 'nsure that the eigen.unctions are physically accepta3le, in 6hich case the correspond2
ing eigen/alues 6ill 3e the possi3le, 0uantised /alues o. the o3ser/a3le7
At is the process o. choosing the appropriate operator 6here a postulate is made 6hich
can only 3e tested against eperiment7 An .ormulating classical mechanics ;e6ton made
the three postulates descri3ed in Section 2727 To interpret the motion o. the planets he
added a .ourth postulate, gra/itational attraction, and then demonstrated that these postu2
lates 6ere appropriate 3y sho6ing that the data .or the motion o. the planets around the
sun could 3e accurately reproduced 3y a mathematical model o. planetary motion 3ased
upon them7 An @ust the same 6ay, SchroM dinger postulated the .orm o. the operator
that 6ould ha/e as its eigen/alues the possi3le energies o. the electron in a hydrogen
atom and tested his postulate 3y calculating the hydrogen atom spectrum7 At the same
time he sho6ed the 6ay in 6hich the operators re0uired .or all the other 0uantum2
mechanical pro3lems o. interest in chemistry can 3e o3tained (Section ,7#,+7 An order
to illustrate
*0 The Application o. &uantum Cechanics
SchroM dingerGs method 6e shall consider t6o pro3lems 6hich, though they are
idealised and simple, also ha/e interesting chemical applications7 The pro3lems concern
the 0uan2 tum mechanics o. an electron conLned to mo/e 6ithin a one2dimensional 3o
or around a ring7
'1' AN E5ECTR2N 2N A RIN
Dollo6ing SchroM dingerGs method, our Lrst tas4 is to determine the .orm o. the energy
oper2 ator7 This operator is called the 8amiltonian, a.ter William :o6an 9amilton (#%05 I
#%?5+ 6ho de/eloped a .ormulation o. classical mechanics in 6hich the relationship o. the
latter
to 0uantum mechanics can 3e most clearly recognised7 We shall 6rite it as 9

7
'1'1% T$e Hamiltonian operator "or t$e ele#tron on a ring
Consider an electron o. mass m
e
6hich is conLned to mo/e at /elocity v
e
in a circular
path o. radius r (Digure ,7#+7 There is no positi/e charge at the centre o. the circle, as
there is in the Bohr model o. the atom, so the electron has only 4inetic energy7 A. the
electron o3eyed the la6s o. classical mechanics its energy 6ould 3e1
E
=
#
m
e
v
2
=
!m
e
v
e
r"
2
,2m
e
r
2
!,.,.#"
2
e
We 6rite the epression .or the classical 4inetic energy in the a3o/e, more complicated,
6ay 3ecause SchroM dingerGs recipe .or Lnding a 0uantum2mechanical operator
depends upon Lrst 6riting do6n the classical mechanical epression .or the o3ser/a3le in
0uestion, in this case the 4inetic energy, and then trans.orming it to the re0uired operator
3y means o. a set o. rules7 An this case 6e note that the 0uantity !m
e
v
e
r"
2
is the s0uare o.
the angular momentum o. the electron (see Chapter *+ and SchroM dingerGs postulate .or
o3taining the
operator corresponding to angular momentum s0uared, l
2
, is1
l
2
= !m
e
v
e
r"
2
l
2
= !h,2( "
2
D
2
,D $
2
!,.,.2"
That is, 6e .orm the operator 3y replacing the classical epression .or the s0uare o. the
angular momentum 3y h`
2
{h`
h,2( } times the second deri/ati/e o. the 6a/e2
.unction
6ith respect to $, the angle deLning the position o. the electron as it tra/els around the
ring7 :ules .or .orming other operators 6ill 3e gi/en as the need arises7 Thus, 6e re0uire
e
m
r
.
6ig;re '1% An electron on a ring
e
An 'lectron on a :ing *#
the eigen/alues (E
n
+ and eigen.unctions (
n
+ 6hich sol/e the e0uation1
h`
2
9


n

2m r
2

D
2

n
D$
=
E
n

n
!,.,.,"
As a3o/e, the su3script n 6ill 3e used to characterise the eigen.unctions and the
associated eigen/alues, o. 6hich there are usually a large num3er7 At must 3e emphasised
that the .orm o. the operator is a postulate7 Although SchroM dingerGs method ma4es
use o. a .ormula .rom classical mechanics as a stepping stone in o3taining the operator, the
relationship 3et6een the classical epression and the 0uantum operator is %ost1lated 1 the
operator is not derived .rom classical mechanics7 The proo. o. the /alidity o. the postulate
lies in the results 6hich it gi/es and 6hich 6e no6 determine7
'1'1& Sol;tion o" t$e S#$roC /inger e@;ation
An the second o. SchroM dingerGs three steps, 6e no6 see4 a .unction 6hich, i. it is to
3e an eigen.unction, must 3e such that 6hen di..erentiated t6ice 6ith respect to the
/aria3le $ it returns to its original .orm7 T6o .unctions 6ith @ust this property spring
readily to mindP sin(a$+ and cos(a$+, 6here a is a num3er (Bo ,7#+1
D
2
!sin a$",D $
2
= aD !cos a$",D $ = a
2
sin a$
D
2
!cos a$",D $
2
= aD !sin a$",D $ = a
2
cos a$
'ither o. these .unctions is an eigen.unction o. the operator 6ith an eigen/alue o.
a
2
h
`
2
,2m
e
r
2
3ecause1
#

2m
e
r
2
h`
2

D
2
sin!a$"
D
2
$
=
a
2
h`
2
2m
e
r
2
sin!a$" !,.,.*"
6ith a /ery similar result .or the cosine .unction7
There.ore, the energy o. our system is a
2
h`
2
,2m
e
r
2
7 9o6e/er, a momentGs
consideration sho6s that 6e are not yet home and dry7 Though h and m
e
are Led, natural
constants and the radius (r + 6ould 3e Led .or any particular pro3lem, no restriction
has 3een placed
upon the constant a7 Conse0uently, any desired energy can 3e o3tained 6ith a suita3le
choice o. the /alue o. aP i7e7 there is as yet no 0uantisation7 We must no6 proceed to
SchroM dingerGs third step and eamine the eigen.unctions sin(a$+ and cos(a$+ to see
i. they are physically accepta3le7
'1'1' T$e a##epta?le eigen";n#tions
The meaning o. the eigen/alues o. SchroM dingerGs e0uations 6as clear .rom the start
and ne/er appears to ha/e presented the pioneers o. 0uantum mechanics 6ith any
di.Lculties7 The interpretation o. the eigen.unctions, on the other hand, raised many
philosophical pro3lems a3out 6hich argument and discussion still continue more than
-5 years a.ter SchroM dingerGs Lrst pu3lication o. his ne6 mechanics7 9o6e/er, 6e shall
adopt the inter2 pretation Lrst suggested 3y Ca Born (#%%2 I #$-0+ in #$2?7 This is
the /ie6 ta4en in all chemical applications o. 0uantum mechanics7 Born proposed that
*2 The Application o. &uantum Cechanics
the s71are o. the eigen.unction, e/aluated at any point in space, gi/es the %ro*a*ility o.
Lnding the particle
descri3ed 3y that eigen.unction at that particular point7 An interpreting the eigen.unction
in this 6ay Born too4 a /ery .undamental step7 9e a3andoned the classical certainty o. a
precise position .or the particle and introduced in its place the concept o. the pro3a3ility
o. Lnding a particle at any particular point in space7 The signiLcance o. this departure
.rom the certainty o. classical mechanics cannot 3e eaggerated7
Thus, i. a particular /alue o. the angle $ is chosen and the eigen.unctions sin(a$+
and cos(a$+ o. the particle on a ring at that point e/aluated, then the s0uare o. the result
gi/es the pro3a3ility o. Lnding the electron at that point in its endless @ourney around the
ring7 Dor a concrete eample, i. a /alue a = *.% is chosen, the .unctions sin(*.%$+ and
Zsin(*.%$+\
2
plotted against $ .or /alues o. $ .rom 0 to ca7 ,( are sho6n in Digure ,727
We note that the eigen.unction itsel. has regions o. 3oth positi/e and negati/e sign, i7e7
it has the property o. phase7 But the pro3a3ility .unction, the s0uared eigen.unction, is
al6ays positi/e as it must 3e i. it represents pro3a3ility7 =sing Digure ,72 6e can readily
Lnd the /alue o. the eigen.unction .or any /alue o. $ and hence determine the pro3a3ility
that the electron can 3e .ound at that particular position around the ring7 But the linear
$2ais o. Digure ,72 conceals, or rather does not ma4e o3/ious, a .undamental deLciency
in the eigen.unction sin(*.%$+7 Digure ,7, in 6hich the .unction is plotted on a dotted
circle (positi/e /alues outside the circle, negati/e /alues inside+ sho6s that 6hen the
angle $ has reached the /alue o. 2( and the electron 3egins a ne6 circuit o. the ring
another, di..erent /alue o. the eigen.unction is o3tained .or the same position on the ring7
To 3e speciLcP sin!*.%$" = 0.0 .or $ = 0 3ut .or $ = 2( , sin!*.%$" = 0.$5#7 "n the
Born model this 6ould imply that the pro3a3ility o. Lnding the electron at the same place
on the ring is proportional
]
to t6o di..erent num3ers, 070 and !0.$5#"
2
= 0.$0*7 This
#70
075
070
075
#70
sin(*7%.+
0 2 * ? % #0
Angle . (radians+
#70
07%
07?
07*
sin
2
(*7%.+
072
070
0 2 * ? % #0
Angle . (radians+
6ig;re '1& Linear plot o. sin(*.%$+ and Zsin!*.%$"\
2
]
We use the 6ord QproportionalG 3ecause the 6a/e .unction still has to 3e multiplied 3y a .actor 6hich 6e shall eplain and
determine in Section ,757
$0
#20 ?0
#50 ,0
#%0 0
2#0
,,0
2*0
2-0
,00
6ig;re '1' Circular plot o. sin(*.%$+, $ = 0 ca72.5(
$0
#20 ?0
#50 ,0
#%0 0
2#0
,,0
2*0
2-0
,00
6ig;re '1( Circular plot o. sin(*.%$+, no limit on $
cannot 3e so7 9ence, though the eigen.unction is per.ectly accepta3le mathematically, it
is %hysically 0uite unaccepta3le7 To 3e physically accepta3le, an eigen.unction must ha/e
only one /alue (i.e. it m1st *e single+val1ed + at any point7 Another 6ay o. loo4ing at the
result is sho6n in Digure ,7*7 A. 6e plot the eigen.unction against $ 6ith no upper limit
on $, 6e disco/er that a.ter L/e cycles around the ring the /alue o. the eigen.unction
3egins to repeat itsel. and a rather pretty pattern results7 A detailed eamination re/eals
that at any /alue o. $ there are L/e /alues o. the eigen.unction 6hich are such that their
sum is e0ual to Kero7 Thus the phases o. the eigen.unction cancel each other gi/ing a
total o. Kero and hence Kero pro3a3ility7 An the language o. 6a/es, 6e 6ould say that the
.unction has 3een reduced to Kero 3y destructi/e inter.erence7
The only physically reasona3le eigen.unctions are ones .or 6hich the /alue at $ = 0 is
e0ual to the /alue at $ = 2( *( . . . (Digure ,75+7 What does this mean .or our eigen.unc2
tions and eigen/aluesJ 9o6 does this re0uirement restrict the /alue o. aJ We re0uire that1
sin!a$" = sin!aZ$ + 2( \" = sin!a$ + 2a( " = sin!a$" cos!2a( " + cos!a$" sin!2a( "
$0
#20 ?0
#50 ,0
#%0 0
2#0
,,0
6ig;re '1) Circular plot o. sin(5$+
2*0
2-0
,00
Clearly, the e0uality 6ill 3e achie/ed i. cos!2a( " = #.0 and sin!2a( " = 0.0, 6hich
is only true 6hen a = 0 # 2 , . . . There.ore, i. the eigen.unctions are to 3e physically
reasona3le a must 3e Kero or an integer and the corresponding eigen.unctions are gi/en 3y1

sin a
= sin!a$" and
cos a
= cos!a$" !,.,.5"
and the energies 3y1
.or 3oth eigen.unctions7
E
a
= a
2
h`
2
,2m
e
r
2
!,.,.?"
Thus, 0uantisation has arisen in the most natural 6ay, as a result o. the re0uirement that
our eigen.unctions should 3e physically reasona3le on BornGs model7 Digure ,75 sho6s
the .unction = sin!5$" in the circular .orm in 6hich a 6hole num3er o. cycles o.
the .unction Lt eactly into the circular path7 At is no6 natural to interpret our integer
a as the num3er n, 6hich 6e introduced in '0uations (,7#72+ and (,7,7,+ to allo6 .or
the .act that there may 3e many eigen.unctions and eigen/alues o. the same operator7 An
this eample the accepta3ility o. the eigen.unction 6as determined 3y the re0uirement
that it 3e single2/alued7 Since the pro3a3ility must 3e smoothly continuous and Lnite, in
order to 3e physically accepta3le, the Born model also places the general re0uirements
on eigen.unctions that they too must 3e continuous and Lnite e/ery6here7
At is interesting to note that the energy le/els occur in pairs o. e0ual energy (Digure ,75+,
one le/el corresponding to the sine eigen.unction and the other to the cosine eigen.unction7
An 0uantum2mechanical parlance, such le/els are said to 3e degenerate7 An Section ,7-72
6e shall disco/er the .undamental origin o. this degeneracy7 Dor a = 0 there is only
one eigen.unction, the cosine .unction (since sin!0" = 0+, and there.ore only one lo6est
energy le/el o. Kero energy7
'1( HU
C
C=E5S F(# ) &G RU5E:
AR2MATICITY
At 6as stated a3o/e that, although the 0uantum2mechanical pro3lems to 3e discussed in
this chapter 6ere simple ones, they ne/ertheless thro6 /alua3le light upon chemical
pro3lems7 The 0uantum2mechanical description o. the electron conLned to mo/e on a ring
9uM c4elGs (*N + 2+ :ule1 Aromaticity *5
pro/ides a 3asis .or 9uM c4elGs (*N + 2+ rule .or the aromatic hydrocar3ons7 :ecall
that the aromatic hydrocar3ons, e7g7 3enKene, naphthalene, anthracene, phenanthrene etc7,
ha/e
? #0 #* . . . = !*N + 2" con@ugated car3on atoms, 6here N = # 2 , . . . (Digure ,7-+7
At is generally accepted that the particular sta3ility o. these molecules depends upon the
presence o. a ( 2electron system, and that each car3on atom contri3utes one electron to
this system, i7e7 the num3er o. ( 2electrons in an aromatic hydrocar3on is e0ual to the
num3er o. car3on atoms (*N + 2+7 (The 9uM c4el theory o. ( 2electron systems is
discussed
in detail in Chapter #27+ An many o. these molecules, especially the smaller ones, all the
car3on atoms lie on the periphery o. the car3on2atom s4eleton and 6e can approimate
the se0uence o. car3on atoms to a ring around 6hich the delocalised ( 2electrons may
circulate 6hile the remainder o. the 3onding electrons are localised in the CIC and
CI9 3onds7 An this model, the energy2le/el scheme .or the ( 2electrons is that sho6n in
Digure ,7? and i. 6e Lll the le/els 6ith electrons, t6o per le/el (the !auli principle+,
'nergy in units
o. h
2
H%p
2
m
e
r
2
25 n = 5
#?
n = *
$ n = ,
* n = 2
#
0
N cos(n.+ N sin(n.+
n = #
n = 0
6ig;re '1* The energy le/els .or an electron on a ring
BenKene
Anthracene
;aphthalene
!henanthrene
6ig;re '1+ The structures o. some o. the smaller aromatic hydrocar3ons
*? The Application o. &uantum Cechanics
2
starting .rom the lo6est (the au.3au principle+, then it is easy to see that to produce a
sta3le conLguration in 6hich all le/els up to a particular energy are completely Llled
re0uires (*N + 2+ electrons7
This concept goes a long 6ay to6ards eplaining the particular sta3ility o. the aromatic
hydrocar3ons7 An #$*$ the idea 6as ta4en .urther 3y John :7 !latt (#$#% I + 6ho used
the electron2on2a2ring model to account .or and classi.y the electronic spectra o. the
aromatic hydrocar3ons (see !ro3lem ?+7 9is classiLcation is 6idely used 3y
spectroscopists and photochemists7
'1) N2RMA5ISATI2N AN3 2RTH22NA5ITY (B"F ,72+
We ha/e not yet completed the tas4 o. ensuring that our eigen.unctions are physically
reasona3le7 A. the s0uare o. an eigen.unction, e/aluated .or any /alue o. $, gi/es the pro32
a3ility o. Lnding the electron at that position on the ring, then the sum o. all such /alues
around the ring must 3e #70 ( certainty+ since, 3y deLnition, the electron is some6here
on the ring7 Since the pro3a3ility distri3ution is a continuous .unction o. the co2ordinates,
the sum 3ecomes an integral o/er the complete range o. all o. them, in 3rie., over all
s%ace7 The process o. ensuring that an eigen.unction gi/es rise to a total pro3a3ility o.
one is 4no6n as the normalisation o. the eigen.unction7 At is an additional re0uirement to
ensure that the chosen mathematical .unctions are also accepta3le physically7 The Lnal,
normalised .orms o. our t6o types o. eigen.unction 6ith the 0uantum num3er no6 6ritten
as n are (see Bo ,72+1

sn
= !#,

(" sin!n$" and


cn
= !#,

(" cos!n$" !n = # 2 , . . ." !,.5.#"


When n = 0, cos 0 = # and .or this .unction the normalising constant is #H

(2( +7
The eigen.unctions o. a 0uantum2mechanical operator ha/e another interesting prop2
erty, orthogonality, 6hich is closely related to normalisation7 The orthogonality o. the
a3o/e eigen.unctions is also demonstrated in Bo ,727
'1* AN E5ECTR2N IN A 5INEAR 82D
An this section 6e eamine the energy2le/els o. an electron conLned 6ithin a one2
dimensional 3oP an idealised situation 6hich also casts signiLcant light on chemical
pro3lems7
'1*1% T$e Hamiltonian operator "or an ele#tron in a linear ?ox
Suppose that 6e ha/e an electron conLned 3y inLnite potential 3arriers 6ithin a one2
dimensional linear 3o o. length L7 We shall again assume that there is no electrostatic
potential present so that the only energy is 4inetic energy7 To construct the appropriate
operator 6e .ollo6 SchroM dingerGs method and Lrst 6rite do6n the classical
epression .or the 4inetic energy in terms o. the momentum, %1
E =
#
m
e
v
2
= !m
e
v"
2
,2m
e
= %
2
,2m
e
e
2
D
An 'lectron in a Linear Bo *-
The postulate .or the con/ersion o. the classical epression .or the s0uare o. the linear
momentum to the appropriate operator is1
2
%
2 2 2 2
7
=
!m
e
v
7
"

%

7
=
h`

D7
2
!,.?.#"
6here 7 = x y or B, the co2ordinate along the 3o7 Thus, the epression .or the 9amil2
tonian operator is1
9

=
!h
`
2
,2m
e
"D
2
,D x
2
!,.?.2"
:ecalling the discussion o. the pro3lem o. an electron on a ring, 6e can guess that the
.unctions1

s*
=
sin!*x" and
c*
=
cos!*x" !,.?.,"
should 3e in/estigated since 3oth are eigen.unctions o. the operator !h`
2
,2m
e
"D
2
,D
x
2
6ith eigen/alues o. *
2
h`
2
,
2m
e
7
'1*1& T$e a##epta?le eigen";n#tions
But are these .unctions physically accepta3leJ We again consider the 3eha/iour o. the
eigen.unctions and in particular their 3eha/iour at x = 0 and x = L, the t6o ends o. the
3o7 Since the electron is, 3y deLnition, conLned 6ithin the 3o, the pro3a3ility o. Lnding
the electron must .all smoothly to Kero at x = 0 and L7 Cos!*x" = #.0 at x = 0 and is
there.ore unaccepta3le on physical grounds7 The sine .unction, ho6e/er, goes smoothly
to Kero as x goes to 0, and the .unction must 3e such that this is also true at x = L7 Since
sin!n( " = 0 6hen n is an integer 6e can satis.y the .oregoing re0uirement i. 6e choose
* so that *L = n( or * = n(,L7 Thus, our only physically accepta3le eigen.unctions o.
the energy operator are1

sn
= N sin!n( x,L" !n = # 2 , . . ." !,.?.*"
6here N is a normalising constant7 The corresponding eigen/alues o. the energy are1
E
n
=

n
2
(
2
L
2

h
`
2

2m
e
n
2
h
2
=
%m L
2
!n
=
# 2 , . . ." !,.?.5"
;ote that n cannot 3e Kero since sin!0" = 0 and there is there.ore no eigen.unction7
Thus, the system never has an energy of Bero, i7e7 it al6ays has some energy and the
presence o. this Bero+%oint energy is an important point to 6hich 6e shall return in
Section ,7##7
An the eigen.unction, the letter * 6hich pre/iously had no particular signiLcance has
no6 3een replaced 3y the 0uantum num3er n (multiplied 3y (,L+7 To Lnd the normalising
constant (N + 6e simply re0uire that the pro3a3ility o. Lnding the electron at any point
along the 3o, summed up, i7e7 integrated, o/er the complete length o. the 3o, is one,
i7e7 that1
L
{N sin!n( x,L"}
0
dx = #.0
This leads to a /alue o. N o.

!2,L" (Bo ,7,+, so our complete set o. physically


accepta3le eigen.unctions is1

sn
=

!2,L" sin!n( x,L" !n = # 2 , . . ." (,7?7?+


*% The Application o. &uantum Cechanics
#%
#?
#*
#2
#0
%
?
*
2
0
0
L
6ig;re '1, 'nergy le/els and eigen.unctions .or an electron in a linear 3o
These .unctions are illustrated .or n = # to * in Digure ,7%7 The ( 2electron spectra o.
linear con@ugated polyenes can 3e interpreted rather 6ell in the light o. these results
(Bo ,7*+7
'1*1' 8o;n/ar0 #on/itions
An selecting a physically accepta3le eigen.unction .rom the /arious possi3le mathematical
solutions o. the SchroM dinger e0uation .or an electron in a linear 3o, 6e made use
o. the .act that the eigen.unction must 3eha/e in an appropriate manner at the ends (3ound2
aries+ o. the 3o7 This led not only to the complete re@ection o. many eigen.unctions
3ut also to the selection o. particular mem3ers o. the set o. sine .unctions, i7e7 those .or
6hich * = n(,L, 6here n is an integer7 At 6as at this point that 0uantisation entered
the pro3lem7 &uantisation is intimately associated 6ith the 3eha/iour o. eigen.unctions
at the 3oundaries o. the system and 6e say that 3oundary conditions are imposed upon
the eigen.unctions to determine those 6hich are physically accepta3le7 An the case o. the
electron on a ring there 6as no o3/ious physical 3oundaryP 3ut the .act that the eigen.unc2
tions 6ere re0uired to ha/e the same /alue at $ = 0 and 2( 6as the 3oundary condition7
Boundary conditions o. this type 4no6n as %eriodic *o1ndary conditions7
'1+ THE 5INEAR AN3 ANU5AR M2MENTA 26 E5ECTR2NS
C2N6INE3 4ITHIN A 2NE93IMENSI2NA5 82D 2R 2N A RIN
An determining the energy le/els in the t6o idealised models descri3ed a3o/e, 6e ha/e
used the linear or angular momentum o. the electron as an intermediate step in the
construction the re0uired energy operator, the 9amiltonian7 An this section 6e return to
consider the momenta themsel/es, and their corresponding eigen/alues and eigen.unc2
tions7 We ta4e the linear system Lrst7
The Linear and Angular Comenta o. 'lectrons *$
'1+1% T$e linear moment;m o" an ele#tron in a ?ox
An Section ,7?7# 6e used the operator .or the s0uare o. the linear momentum o. the
electron in a linear 3o, h`
2
D
2
,D x
2
, in order to .orm the 9amiltonian operator so
that
the operator .or linear momentum appears to 3e readily a/aila3le as the s0uare root o.
h
`
2
D
2
,D x
2
7 But this presents t6o pro3lems7 Dirstly, 6hat is the s0uare root o. D
2
,D x
2
J
This is not di.LcultP D
2
,D x
2
means di..erentiate the .unction t6ice 6ith respect to x, i7e7
!D,D x"

!D,D x", so a single di..erentiation 6ould represent the s0uare root7 The

h
`
2
poses
a greater pro3lem in that 6e ha/e to Lnd the s0uare root o. a negati/e 0uantityU But 6e
do not allo6 such pro3lems to deter usP 6e simply .ollo6 the lead o. the mathematicians
6ho con.ronted this pro3lem many years ago and sol/ed it 3y in/enting a ne6 num3er,
i, the s0uare root o. #P i7e7 i
2
= # (Appendi %+7 9a/ing done this 6e can epress
the s0uare root o. any negati/e num3er, e7g7 !2i"
2
= *, !5.,i"
2
= 2%.0$7 Such
num3ers are called imaginary num3ers and 6ith their aid 6e can 6rite the operator .or
linear momentum as1
D
%
=
ih`

Dx
!,.-.#"
". the t6o possi3le signs .or the s0uare root 6e choose the negati/e one .or reasons
6hich 6ill 3ecome clear 3elo67
A. 6e apply this operator to our energy eigen.unctions
sn
6e see immediately that
they are not eigen.unctions o. the linear momentum operator 3ecause di..erentiation o.
sine gi/es cosine7 What 6e need is a .unction 6hich does not change 6hen di..erentiated
once7 The eponential .unction, e
nx
or ep!nx" is such a .unction (Bo ,7#+ and1
D

ih`

Dx
{
ep!nx"
} =
ih`

n
{
ep!nx"
}
!,.-.2"
We no6 ha/e a mathematical eigen.unction, 3ut there is a serious pro3lem hereP the
calculated /alue o. our linear momentum, inh` , contains a .actor i and is there.ore
an
imaginary 0uantity7 This is 0uite unaccepta3le .or a 0uantity 6hich 6e can measure in
the la3oratory and 6hich must there.ore 3e realU But this can 3e o/ercome i. 6e 6rite
+in in place o. n as the argument o. the eponential .unction 3ecause then1
D

ih`

Dx
{
ep!
+
inx"
} =
ih`

in
{
ep!
+
inx"
} =
nh`
{
ep!
+
inx"
}
(,7-7,+
since i
2
= #7
Thus, the .unction ep(+in + is an eigen.unction o. the linear momentum operator
6ith an eigen/alue o.
+
nh
`
, and 3y choosing the negati/e sign .or the operator 6e ha/e
the result that the sign o. the momentum is the same as that o. the argument o. the
eponential .unction7 We interpret this .unction as descri3ing the motion o. an electron in
the positi/e x2direction 6ith a positi/e /alue o. %
x
7 Similarly, the .unction ep!inx" is an
eigen.unction o. the linear momentum operator 6ith an eigen/alue o.
nh`
and descri3es
an electron mo/ing in the negati/e x2direction7 Durther, 6e should note that these t6o
eponential .unctions are also eigen.unctions o. the energy operator each ha/ing the same
eigen/alue, i7e7 n
2
h`
2
H2m
e
7
But neither o. the eponential .unctions is physically accepta3le .or a 3o o. Lnite
length L1 3oth .ail to satis.y the re0uirement that they must go smoothly to Kero at x = 0
3ecause ep!0" = #.07 There.ore, since the eigen.unctions o. the linear momentum oper2
ator are not accepta3le eigen.unctions .or a 3o o. Lnite length, no linear momentum can
3e measured .or a particle conLned 6ithin such a 3o7 But i. the 3o is inLnitely long then
there are, in e..ect, no 3oundaries and the t6o eponential .unctions are 3oth physically
accepta3le7 But then no restrictions are placed upon the mathematical eigen.unctions and
there is there.ore no 71antisation7 An such a case the eigen/alues o. linear momentum
corresponding to the t6o types o. eigen.unction are1
eigen.unction eigen/alue

+*
= N ep!+i*x" %
+*
= +*h
`

*
=
N ep!

i*x" %
*
=
*h
`
6here * can ha/e any /alue7 The normalisation o. the eigen.unction o. an electron in
an inLnitely long 3o presents some di.Lculties and 6e shall not enter into that su3@ect
here (see Section #27, 6here periodic 3oundary conditions are used+7 The translational
energy 6hich results .rom this linear momentum is, o. course, also un0uantised7 At is the
.orm o. these .unctions that is responsi3le .or the name 6a/e mechanics 6hich is usually
gi/en to 0uantum mechanics in the SchroM dinger .orm7 The eponential .unctions
descri3e electrons mo/ing along x in a positi/e or negati/e direction and the energy
calculated is the 4inetic energy associated 6ith that mo/ement or momentum7 The sine
.unctions ha/e no associated momentum since they are not eigen.unctions o. the
momentum operator7 Anasmuch as they can 3e .ormed as the sum and di..erence o. the t6o
eponential .unctions (Appendi %+ they are standing 6a/es 6hich descri3e electrons
mo/ing in 3oth directions along x 6ith mutually cancelling momenta7 But the energy
is not Kero 3ecause it is proportional to the s0uare o. the momentum7
'1+1& T$e ang;lar moment;m o" an ele#tron on a ring
Dor an introduction to angular momentum see Chapter *7
Since the electron is mo/ing around the ring it has or3ital angular momentum7 To
o3tain the operator .or angular momentum (l

+ 6e .ollo6 the procedure o. the last section


and Lnd1
l

=
ih`

D,D $
!,.-.*"
Where 6e again choose the negati/e s0uare root .or the same reason as in the linear
case7
9ere also 6e Lnd that eponential .unctions are 6hat 6e re0uire and, in particular,
the .unction ep(+in$+ is an eigen.unction o. the angular momentum operator 6ith an
eigen/alue o. +nh` , 6hile the .unction ep(in$+ is also an eigen.unction o. l

6ith an
eigen/alue o. nh` 7 This loo4s encouraging, 6e epect to Lnd e0ual and opposite
/alues
o. the angular momentum since the electron can circle the ring in a cloc46ise (negati/e
a7m7+ or counter2cloc46ise (positi/e a7m7+ direction7
But are the .unctions physically reasona3le, are they single2/aluedJ As the /alue at
$ = 0, .or eample, e0ual to that at $ = 2( J And are they normalisedJ To ans6er the
Lrst 0uestion 6e note the standard results (Appendi %+1
ep!+in$" = cos!n$" + i sin!n$" and ep!in$" = cos!n$" i sin!n$"
We 4no6 .rom our deli3erations a3o/e that the sine and cosine .unctions are 3oth
single2/alued i. n is an integer or Kero7 There.ore, our eponential eigen.unctions o.
0
the angular momentum operator 6ill also 3e single2/alued i. n = 0 # 2 , . . . When
n = 0 the t6o eigen.unctions are one and the same and they ha/e an eigen/alue o. Kero7
Dor all other /alues o. n the system has paired e0ual and opposite /alues o. the angular
momentum7 'ach /alue is an integral multiple o. !lanc4Gs constant di/ided 3y 2( 7 =nli4e
the energy eigen/alues 6hich are determined 3y n
2
, the angular momentum eigen/alues
are determined 3y n and are e/enly spaced (Digure ,7$+7
To normalise the .unctions 6e must ma4e allo6ance .or the .act that they contain
3oth a real term, cos!n$" and an imaginary term i sin!n$"7 An epression 6hich contains
3oth real and imaginary parts is said to 3e com%lex7 Born allo6ed .or this possi3ility in
deLning the meaning o. a 0uantum2mechanical eigen.unction and proposed that in the case
o. comple eigen.unctions the pro3a3ility 6as gi/en, not 3y the s0uare o. the .unction,
3ut 3y the product o. the .unction and its comple con@ugate7 The comple con@ugate o.
any comple .unction is o3tained simply 3y changing +i to i and i to +i e/ery6here
(Appendi %+7 Thus ep!+in$" is the comple con@ugate o. ep!in$", and vice versa7
There.ore, the pro3a3ility, P !$" o. Lnding the electron at a particular angle, $, around
the ring is gi/en 3y1
P !$" = ep!+in$" ep!in$" = ep!0" = #.0
This result tells us t6o important .acts7 Dirstly, the distri3ution o. the electron does not
depend upon the /alue o. $, it is the same at all points around the ring7 But it also sho6s
that the .unction re0uires normalisation (see Bo ,72+ so that the sum o. the pro3a3ilities
all around the ring add up to #707 We Lnd the normalising constant 3y integrating the
epression a3o/e .rom 0 to 2( 7 We Lnd1
2(
ep!+in$" ep!in$" d$ =
0
2(
ep!0" d$ =
0
2(
# d$ = Z$\
2(
= 2(
0
Angular Comentum
in units o. hH2p
(#H2+ep(+in.+ (#H2p+ep(in.+
*
,
2
#
0
n = *
n = ,
n = 2
n = #
n = 0
6ig;re '1- The angular momentum eigen/alues o. an electron on a ring
e
6hich sho6s that each eigen.unction must 3e multiplied 3y

!#,2( "7 There.ore, our Lnal


normalised 6a/e .unctions are1

+n
=

#
2(

ep!
+
in$" and

n
=

#
2(

ep!

in$" (,7-75+
'1, THE EIEN6UNCTI2NS 26 3I66ERENT 2!ERAT2RS
We ha/e determined the eigen/alues and eigen.unctions o. the operators .or the energy
and angular momentum o. an electron conLned to mo/e on a circle o. radius r 7 An so doing
6e ha/e noted that, although the .unctions
sn
=

!#,( "

sin!n$" and
cn
=

!#,( "

cos!n$", 6ith n an integer, are eigen.unctions o. the energy operator, or 9amiltonian, 9



1
2
9

h` =
2m
e
r
2

D
2
,D
2
$
they are not eigen.unctions o. the angular momentum operator1
l

= ih
`
D,D
$
The reason .or this is 0uite clear, the sine and cosine .unctions return to their original
.orm only 6hen di..erentiated t6ice 6ith respect to the angle $7 Whereas an eigen.unction
o. l

must 3e a .unction such as the eponential, the Lrst deri/ati/e o. 6hich is the
eponential .unction itsel. (Bo ,7#+7 A. 6e di..erentiate the eponential .unctions t6ice
6ith respect to $ 6e Lnd that they are also eigen.unctions o. the energy operator 6ith
the same eigen/alues as the sine and cosine .unctionsP e7g71

#

2m
e
r
2
h`
2


#
2(

D
2
D$
2

n
2
h`
2
{
ep!in$"
} =
2m r
2

#

2(
{ep!in$"}
The results are summarised in Ta3le ,7#7
Drom these results 6e can dra6 the important conclusion that it is possi3le .or a system
o3eying the la6s o. 0uantum mechanics to 3e in a state that is descri3ed 3y a .unction
Ta?le '1% The energy and angular momentum o. an electron
on a ring
"3ser/a3le 'nergy Angular momentum
"perator 9

l

Dunction 'igen/alue 'igen/alue


#
2 2 2

(

sin!n$" n
h
`
,2m
e
r not an eigen.unction
#
2 2 2

(

cos!n$" n
h
`
,2m
e
r not an eigen.unction
#
2 2 2

2(

ep!
+
in$" n h` ,2m
e
r
+
nh
`
#
2 2 2

2(

ep!

in$" n
h`
,2m
e
r

nh
`
a

a
'igen.unctions, 'igen/alues and 'perimental Ceasurements 5,
6hich is an eigen.unction o. one operator, 3ut is not an eigen.unction o. some other
operator7 The system may also 3e descri3ed 3y a .unction 6hich is an eigen.unction o.
more than one operator7 Since the eigen/alues o. operators are the o3ser/a3les 6hich 6e
can measure eperimentally, these results place important restrictions on 6hat 6e can
4no6 a3out a system7 This 0uestion 6ill 3e ta4en up again in Section ,7#07
'1- EIEN6UNCTI2NS< EIENVA5UES AN3 ED!ERIMENTA5
MEASUREMENTS
We ha/e seen that the eigen.unctions and eigen/alues 6hich sol/e SchroM dingerGs
e0uation .or a particular system are, respecti/ely, 6a/e .unctions descri3ing the
distri3utions o. the electron(s+ in/ol/ed in the pro3lem and the /alues o. the 0uantised
o3ser/a3les o. the electrons such as energy and momentum7 There is a direct
correspondence 3et6een the mathematical process o. sol/ing SchroM dingerGs e0uation
to o3tain the /alue o. an o3ser/a3le 3y calculation and the measurement o. that
o3ser/a3le in an eperiment7 But 6e ha/e also seen that it is possi3le .or a 0uantum2
mechanical system to 3e descri3ed 3y a .unction 6hich is an eigen.unction o. one
operator 3ut not o. another7 Dor eample,
the .unction
cn
=
!#,

("

cos!n$" is an eigen.unction o. the energy operator .or an
electron on a ring, 3ut it is not an eigen.unction o. the corresponding angular momentum
operator7 We might as4, there.ore, 6hat 6ould 3e the result o. attempting to measure the
angular momentum o. the electron on a ring 6hen it is in the state descri3ed 3y the a3o/e
cosine .unctionJ &uantum mechanics gi/es a clear ans6er to this 0uestion7
Suppose Lrst that 6e measure an o3ser/a3le (r + in a system 6hich is in a state descri3ed
3y an eigen.unction (
a
+ o. the operator (:

+ that corresponds to this o3ser/a3le7
We
call such a state an eigenstate o. :

7 Then the result o. the (idealised and error2
.ree+
measurement 6ill 3e the eigen/alue (r
a
+ corresponding to that eigen.unction and operator,
i7e7 the solution o. the SchroM dinger e0uation1
:


a
= r
a

a
!,.$.#"
And, 6ith the 0ualiLcations to 3e descri3ed 3elo6, 6e shall get the same ans6er, r
a
,
e/ery time 6e repeat the measurement7
A. 6e no6 attempt to measure the same o3ser/a3le in a system 6hich is not in a
state descri3ed 3y an eigen.unction o. the operator
:

corresponding to the o3ser/a3le


r , then the result o. the measurement 6ill still 3e one o. the possi3le eigen/alues o. :

,
3ut 6e cannot say 6hich7 A. 6e repeat the measurement 6e shall, in general, o3tain a
di..erent resultP another eigen/alue o. :

7 A. the measurement is repeated many times,
the
/alue measured each time 6ill al6ays 3e one o. the eigen/alues o. :

, and there
may
3e repetition o. some /alues, 3ut 6e cannot say 6hat /alue any particular measurement
6ill gi/e7 9o6e/er, as the num3er o. measurements increases, the a/erage result o. the
measurements 6ill tend to a /alue (r + 4no6n as the mean /alue, 6hich can 3e calculated
using the .ormula1

r =
all space

:
a
dv

all space


a
dv !,.$.2"
The di/ision 3y


a


a
dv allo6s .or the use o. un2normalised 6a/e .unctions and
the

indicates that 6e ha/e to ta4e the comple con@ugate o.
a
i. it is a comple
5* The Application o. &uantum Cechanics
2
.unction (see Appendi %+7 The integration o/er Qall spaceG means integration o/er the
.ull range o. co2ordinates a/aila3le to the system, e7g7 .rom to + in x y and B7
'0uation (,7$72+ is an important complement to '0uation (,7$7#+7 At pro/ides us 6ith the
means o. calculating a /alue .or an o3ser/a3le e/en 6hen the
a
Gs are not eigen.unctions
o. the operator :

7 r is then the a/erage o. a large num3er o. measurements7 At is
the
result 6hich 6e 6ould ex%ect to get as the mean o. a large num3er o. measurements and
is accordingly called the ex%ectation val1e o. r 7 9ere pro3a3ility again enters into the
predictions o. 0uantum mechanicsP in such circumstances 6e cannot predict the result o.
an indi/idual measurementP the 3est 6e can do is to gi/e the /alue to 6hich the mean o.
a large num3er o. measurements 6ill tend7
Be.ore proceeding to an eample, 6e note that in 0uantum mechanics the idea o.
repeating an eperimental measurement is not a simple concept7 At is one o. the .oundation
stones o. the philosophy o. 0uantum mechanics that, in general, a system is a..ected 3y
any measurement made upon itP its state, and the 6a/e .unction 6hich descri3es it, may
not 3e the same a.ter the measurement as they 6ere 3e.ore it7 There.ore, a.ter each
measurement the system must 3e allo6ed to return to its original state 3e.ore the net
measurement can 3e made7 This is a point 6hich 6e shall discuss in detail in the net
section7 Since, in chemistry, a sample su3@ected to a measurement usually consists o. a
/ery large num3er (

#0
2,
+ o. identical molecules or atoms, 6e may consider in such
cases that the result o3tained is the mean /alue deLned as a3o/e 3ut that it is o3tained as
the result o. the same measurement made simultaneously upon many identical systems7
By 6ay o. an eample, in Bo ,75 6e use '0uation (,7$72+ to determine the epectation
/alue .or the angular momentum o. an electron on a ring 6hen it is in the cosine .unction
state7 The result o. Kero may at Lrst appear unli4ely, 3ut it is 0uite easy to understand7
According to Appendi %1
cos!n$" =
#
{ep!+in$" + ep!in$"} !,.$.,"
Thus, the cosine .unction is composed o. e0ual parts o. the t6o eponential .unctions
6hich are the eigen.unctions o. the angular momentum operator7 Since the t6o eigen.unc2
tions ha/e e0ual and opposite angular momenta (Ta3le ,7#+ the com3ination o. the t6o
gi/es an epectation /alue o. Kero7 Thus, an eperimental measurement o. the angular
momentum 6hen the electron is in the cosine .unction state may gi/e a /alue o.
+
nh`
or o.

nh
`
7 But i. many measurements are made the t6o /alues 6ill occur 6ith
e0ual
pro3a3ility and the mean result 6ill tend to the /alue o. Kero7 Alternati/ely, as noted
a3o/e, i. the sample is a typical QchemicalG one and contains a /ery large num3er o.
atoms or molecules then the result o. one measurement on the sample as a 6hole, i7e7
simultaneously on many indi/idual atoms (molecules+, may 3e regarded as the a/erage
o. many se0uential measurements on an indi/idual atom (molecule+7
'0uation (,7$72+ is o. particular /alue in pro3lems 6here 6e ha/e di.Lculty in sol/ing
SchroM dingerGs e0uation and o3taining its eigen.unctions7 Because o. the compleity
o. many chemical systems, it is normally impossi3le to sol/e '0uation (,7$7#+ directly7
=nder such circumstances it is use.ul i. 6e can postulate an approimate 6a/e .unction .or
the system and use that to determine an approimation to the o3ser/a3le 0uantities 3y
means o. '0uation (,7$72+7 This type o. calculation plays an essential role in the theory o.
the chemical 3ond as 6e shall see in Chapter ?7
Core A3out Ceasurement1 The 9eisen3erg =ncertainty !rinciple 55
'1%. M2RE A82UT MEASUREMENT: THE HEISEN8ER
UNCERTAINTY !RINCI!5E
An Section ,7$ 6e noted that it is a .undamental 0uantum2mechanical principle that no
measurement can 3e made upon a system 6ithout a..ecting that system7 This should not
really surprise us7 Suppose that 6e 6ish to measure the time at 6hich a locomoti/e passes
a particular point on a rail6ay line, there3y Ling its position at that particular time7 We
might stretch a cotton thread attached to a timing mechanism across the trac47 There
6ould 3e no concern that the collision o. the locomoti/e 6ith the thread 6ould slo6 the
train to any degree 6hich could 3e measured7 This 3eing so, a second de/ice o. the same
type placed a 4no6n distance do6n the trac4 6ould ena3le us to L the position o. the
locomoti/e .or a second time and measure its a/erage /elocity 3et6een those t6o points
on the line and, i. 6e 4no6 its mass, its mean linear momentum7
But 6hat i. the mo/ing o3@ect to 3e timed 6as a OyJ A. the mechanism 6as su.Lciently
delicate 6e might 3e a3le to determine the time at 6hich the Oy struc4 the Lrst timing
de/ice, 3ut 6e certainly could not maintain that the OyGs .urther progress 6ould 3e
una..ected 3y its contact 6ith the thread7 Thus, a measurement o. its mean /elocity or
momentum 6ould 3e in/alidated since it 6ould not 3e independent o. the measurement
itsel.7 An the case o. the Oy, the pro3lem could 3e o/ercome 3y using 3eams o. light and
photocells in place o. the mechanical timing de/ices7
But 6hat i. the o3@ect to 3e studied 6as an electronJ 'lectrons are not indi..erent to
photonsP as 6e sa6 in Section 27?, electrons can 3e e@ected .rom metals 3y photons7 Thus,
6e could not 3e sure i. the impact o. the QmeasuringG photon had changed the position o.
the electron, its /elocity, or 3oth7 There are no means 3y 6hich e/ents at the atomic and
molecular le/el can 3e o3ser/ed in such a 6ay that those e/ents are not inOuenced 3y the
5? The Application o. &uantum Cechanics
act o. o3ser/ation itsel.7 Just as in sociology, 6here merely to as4 a particular 0uestion
has an inOuence upon the respondentGs attitude to that su3@ect, there is no uninOuential
o3ser/ation in 0uantum mechanics7
-o o*serve a system is to interact 0ith it and change it.
An .act, the pro3lem o. the accuracy o. measurement is e/en more su3tle than the
a3o/e discussion suggests7 An #$2- 9eisen3erg sho6ed that, in systems o3eying the la6s
o. 0uantum mechanics, there are pairs o. related properties 6hich cannot 3e measured
eactly at the same time (Bo ,7?+7 This situation is .undamental to 0uantum2mechanical
systems and 9eisen3erg epressed the result in the .orm o. his uncertainty principle, an
eample o. 6hich is1
%
x

x

h,*(
!,.#0.#"
%
x
is the uncertainty in the result o. a measurement o. the linear momentum o. a
particle along x and x is the uncertainty in the measurement o. the x co2ordinate,
and their product has to 3e greater than !lanc4Gs constant di/ided 3y *( 7 "ther pairs o.
o3ser/a3les lin4ed 3y an uncertainty relationship are gi/en in Bo ,7?7 At is important
to note that this uncertainty o. measurement has nothing to do 6ith the 0uality and
precision o. the e0uipment a/aila3le .or the measurement, nor 6ith the a3ility o. the
eperimentalist7 The limitation on the measurement is .undamental and '0uation (,7#07#+
assumes that per.ect eperimental de/ices are used 3y per.ect eperimentalists7 Thus, to
return to the pro3lem o. the Oy, the pro3lem o. getting the Oy to hit the timing de/ice is
0uite irrele/ant to the argument here7
The magnitude o. !lanc4Gs constant and its presence in '0uation (,7#07#+ eplains 6hy
the conse0uences o. the uncertainty principle 6ere ne/er noticed in classical mechanics7
Since the product o. the t6o uncertainties is a3out one order o. magnitude less than
!lanc4Gs constant it is so small that the indi/idual uncertainties in the /alues o. position
and momentum are much too small to 3e o3ser/ed in an eperiment 6ith macroscopic
3odies7 A. 6e di/ide 3oth sides o. '0uation (,7#07#+ 3y, m, the mass o. the particle
concerned, 6e o3tain1
v
x

x

h,*(m !,.#0.2"
The Commutation o. "perators 5-
6hich sho6s clearly ho6 the product o. the t6o uncertainties 3ecomes smaller as the mass
o. the particle increases, i7e7 as 6e go .rom systems 6hich re0uire a 0uantum2mechanical
description to those to 6hich classical mechanics applies7 ;ote that the 0uantity on the
right2hand side o. the ine0uality (,7#07#+ is not al6ays gi/en as h,*( , it is 0uite common
to Lnd h,2( .or eample7 These di..erences are a conse0uence o. the di..erent 6ays in
6hich the uncertainties %
x
and x can 3e deLned, 3ut this in no 6ay in/alidates the
.undamental uncertainty principle 6hich 9eisen3erg Lrst enunciated7 The particular /alue
o. h,*( applies to the case 6here the uncertainties are assumed to .ollo6 the Gaussian
distri3ution la67
'1%% THE C2MMUTATI2N 26 2!ERAT2RS (B"F'S 272 A;< ,7?+
An Section ,7#0 6e recognised that there are important limitations on 6hat 6e can 4no6
a3out a system 6hich o3eys the la6s o. 0uantum mechanics7 An particular 6e sa6 that the
accuracy 6ith 6hich the t6o properties, momentum in the x direction and x co2ordinate,
could 3e simultaneously measured, 6as restricted 3y the 9eisen3erg uncertainty principle7
We discussed the matter .rom an essentially eperimental point o. /ie6P no6 6e loo4 at
the pro3lem .rom the theoretical standpoint7
According to Section ,7$, e/ery o3ser/a3le 0uantity has an associated operator 3y
means o. 6hich either the eact /alue o. the o3ser/a3le or a mean /alue can 3e calculated
using '0uations (,7$7#+ or (,7$72+ respecti/ely7 9o6 6ould the pro3lem o. calc1lating t6o
properties 3e .ormulatedJ At seems natural to suggest that, in direct correspondence 6ith
eperimental measurement, 6e Lrst calculate the one and then the other7 Thus, i. 6e ha/e
a system in the state
a
.or 6hich 6e 6ish to 4no6 the simultaneous /alues o. t6o
properties P and 3 6e could per.orm the calculation1
P

3


a
= P

7
a

a
= 7
a
P


a
= 7
a
%
a

a
or
3

P


a
= 3

%
a

a
= %
a
3


a
= %
a
7
a

a
And since %
a
and 7
a
are simply num3ers 6e o3tain the same result, regardless o.
the order o. application o. P

and 3

7 But these t6o calculations assume that
a
is
an eigen.unction o. 3oth P

and
3

6hich is 3y no means al6ays the case7 This can 3e


illustrated using the momentum and position operators and the eigen.unction .or a electron
in an inLnitely long 3o .rom Section ,7-7#1
+
*
= N ep!+i*x"7
The operator .or linear momentum along x is

ih
`
D,D x and the operator .or the x
co2ordinate is x itsel. and 6e in/estigate the e..ect o. applying these t6o operators
consecuti/ely to the a3o/e eigen.unction7 We ha/e either1
D D
x

!

ih` "
Dx

+
*
=
ih` N x
Dx
ep!
+
i*x"
=
ih` N xi* ep!
+
i*x"
=
h` *x
+
*
or
D D

ih`
Dx
x


+
*
=
ih` N
Dx
x ep!
+
i*x"
=
ih` N
{
ep!
+
i*x"
+
xi* ep!
+
i*x"
}
=
ih
`

+*
+
h
`
*x
+*
The results are not the same, in .act1
!x %
x
%
x
x "
+
*
= ih`
+
*
!,.##.#"
5% The Application o. &uantum Cechanics
When the t6o results .or the consecuti/e operation o. t6o operators are not e0ual
6e say that the operators do not commute and the root o. the pro3lem lies in the .act
that it is not possi3le to Lnd a .unction 6hich is simultaneously an eigen.unction o.
3oth operators7 As a conse0uence, it is not possi3le to 4no6, simultaneously, 3oth the
o3ser/a3les associated 6ith the operators7 Thus, 9eisen3ergGs uncertainty principle is a
mani.estation o. the .act that the operators corresponding to the t6o o3ser/a3les in/ol/ed
do not commute7
We can see some o. the e..ects o. 9eisen3ergGs uncertainty principle in relation to
position and momentum along the x co2ordinate using, once more, our pair o. eponential
6a/e .unctions .or the electron in a linear 3o7 The pro3a3ility, P !x

+, o. Lnding an
electron at a point ha/ing the co2ordinate x

is proportional to the product o. the 6a/e
.unction and its comple con@ugate e/aluated at that point, i7e71
P !x

" = N
2
ep!i*x

" ep!+i*x

" = N
2
ep!0" = N
2
6here N is the normalising constant7 The important point here is that the pro3a3ility is the
same at e/ery point along the 3o, since it does not depend upon x7 Thus, .or an inLnitely
long 3o the uncertainty in our 4no6ledge o. the position o. the electron is inLnite since it
can 3e any6here in the 3o7 But it is only .or a 3o o. inLnite length that the momentum
has the eact /alues o. *h,2( 7 Thus, .or the inLnitely long 3o the linear momentum
o. the electron is 4no6n eactly 3ut the uncertainty in its position is inLnite7 Dor any 3o
o. Lnite length the uncertainty in our 4no6ledge o. the position o. the electron is Lnite,
since then it must lie 3et6een 0 and L7 There.ore, there must also 3e a Lnite uncertainty
in our 4no6ledge o. the momentum o. the electron7 Durther, since there is no potential
energy term in the pro3lem, the energy is all 4inetic energy and there.ore proportional to
the s0uare o. the momentum so that the energy o. the electron must also 3e uncertain7
There could 3e no uncertainty i. the energy 6as Kero, so the .act that there is a Kero2point
energy (Section ,7?72+ is in accord 6ith the 9eisen3erg uncertainty principle7
'1%& C2M8INATI2NS 26 EIEN6UNCTI2NS
AN3 THE SU!ER!2SITI2N 26 STATES
An Section ,7$ 6e sa6 that a .unction 6hich 6as not an eigen.unction o. the angular
momentum operator .or the electron on a ring could 3e 6ritten as a sum o. t6o eigen2
.unctions o. that operator ('0uation (,7$7,++7 This is an important result 6hich may 3e
generalised .urther7 Any .unction 6hich o3eys the 3oundary conditions (Section ,7?7,+ o.
a pro3lem can 3e epressed as a sum o. the eigen.unctions o. that pro3lem7 The /alue
o. this result lies in the 6ay in 6hich it allo6s us to address the .ollo6ing pro3lem7 We
4no6 that an atom (or molecule+ may eist in an electronic eigenstate o. the 9amiltonian
operator7 An this state it has a precisely measura3le energy7 We also 4no6 that i. light o.
an appropriate .re0uency stri4es the atom it may a3sor3 a photon and ma4e a transition
to an eigenstate o. higher energy and that this process ta4es a Lnite time7 'stimates o. the
time re0uired are discussed in Chapter %, 3ut 6e may say here that it is o. the order o.
#0

#%
s7 But 6hat is the appropriate description o. the atom during the time in 6hich it
has le.t the initial eigenstate, G
i
, 3ut has not yet arri/ed in the Lnal eigenstate, G
f
J Since
3oth G
i
and G
f
are eigen.unctions o. the same 9amiltonian operator, any other state o.
the atom, 6hich is not an eigenstate, may 3e descri3ed as a sum, suita3ly normalised,
"perators and their Dormulation 5$
o. these t6o states plus contri3utions .rom all the other eigenstates o. the 9amiltonian
operator .or the atom7 The technical term .or such a description is a s1%er%osition of
states7 An this particular pro3lem it is reasona3le to assume that the contri3utions .rom
the other eigenstates are /anishingly small so that at any moment during the transition
the atom is in the state H , 6here H can 3e approimated as a superposition o. @ust t6o
states, i7e71
H
=
c
i
G
i
+
c
f
G
f
!,.#2.#"
And, assuming that the .unctions G
i
and G
f
are orthogonal and normalised, H 6ill 3e
normalised i.1
c
2 2
i
+
c
f
=
#.0 !,.#2.2"
Be.ore the photon stri4es the atom, c
i
= #.0 and c
f
= 0.07 When the process o. a3sor32
ing the photon is complete, c
i
= 0.0 and c
f
= #.07 At any point in time during the
a3sorption process, c
i
is decreasing and c
f
increasing, su3@ect al6ays to the normalisa2
tion condition ('0uation (,7#272++7 Thus the system undergoing a spectroscopic transition
does not enter some .orm o. lim3o a3out 6hich 6e 4no6 nothingP 6e ha/e a description
o. the system throughout the process7 This description o. the a3sorption or emission o. a
photon is eamined in more detail in Section %7?7
'1%' 2!ERAT2RS AN3 THEIR 62RMU5ATI2N
At has 3een emphasised a3o/e that the .orm o. the operator .or any particular o3ser/a3le
is a postulate 6hich has 3een tested against its success in calculations o. measura3le
0uantities using that operator7 Since classical mechanics is a limiting case o. 0uantum
mechanics, 6e might epect that relationships 3et6een operators thus deri/ed 6ould
reOect the relationships 3et6een the corresponding classical 0uantities7 This is indeed the
case and use can 3e made o. that .act in the construction o. operators7 As .ar as the usual
chemical applications o. 0uantum mechanics are concerned, the operators .or position
(co2ordinate+, potential energy, 4inetic energy, linear momentum and angular momentum,
play 3y .ar the most important roles7 The relationships 3et6een these operators mirror
the relationships o. the corresponding classical 0uantities as the .ollo6ing 6ill sho67
'1%'1% !osition or #o9or/inate< ()
The operator .or the position o. a particle, x or r say, is simply x
or r7 Where the
caret mar4 (+ is used to distinguish the operator .rom the o3ser/a3le7 There.ore, the
epectation /alue (x+ o. the x co2ordinate o. a particle descri3ed 3y the normalised 6a/e
.unction G is1

x =
all space
G x G dx dy dB G |x |G
using the notation introduced 3y <irac7
'1%'1& !otential energ0< *
)
Since potential energy is in/aria3ly epressed in terms o. the position o. a particle in
some Leld o. .orce, e7g7 the distance o. the electron .rom the nucleus in the hydrogen
?0 The Application o. &uantum Cechanics
x x x
Dx
2
atom or the angle 3et6een a nuclear magnet and an applied magnetic Leld, the essential
operator in potential energy is the position operator7 There.ore, using the result a3o/e, the
classical epression .or the potential energy (V + o. t6o charges o. +e and e separated
3y a distance r is replaced 3y the operator V

in the .ollo6ing 6ay1


V = e
2
,r V

= e
2
,r
'1%'1' 5inear moment;m< p)
(
We ha/e already seen that linear momentum in the x direction is replaced in the operator
.ormalism 3y di..erentiation 6ith respect to x multiplied 3y ih,2( , i7e71
p = mv p = ih`

DG
'1%'1( =ineti# energ0< W
)
We deduce the .orm o. the 4inetic energy operator 3y epressing 4inetic energy as the
s0uare o. the momentum di/ided 3y mass and using the last result, i7e71
W
=
#
mv
2
=
!mv
x
"

W
h
`
2
=
D
2
G

2 x
2m 2m Dx
2
'1%'1) Ang;lar moment;m< L
)
The angular momentum (see also Chapter *+ o. a particle o. mass m rotating a3out a
centre is the /ector product o. the distance o. the particle .rom the centre (r+ and its linear
momentum (p+7 A. the rotation ta4es place in the xy2plane (B
=
0 %
B
=
0+, then resol/ing
the /ectors r and p into their Cartesian components, 6e ha/e our angular momentum
operator as1
DG DG

L
=
r

p
=
x%
y

y%
x

L

=
ih
`
x

Dy

y

Dx
'1%( SUMMARY
An this chapter 6e ha/e studied the application o. 0uantum mechanics to simple pro3lems
and ha/e 3een particularly concerned to eamine the eact details o. the description o.
the 6orld o. atoms and molecules 6hich the method pro/ides7 This di..ers .rom the
description o. the macroscopic 6orld gi/en 3y classical mechanics in a num3er o. /ery
important 6ays and, on the .ace o. it, 6e appear to ha/e less in.ormation a/aila3le to us
6hen 6e use 0uantum mechanics than 6e ha/e 6hen 6e use classical mechanics7 With
this in mind, it is essential that 6e .ocus our attention upon things 6hich can 3e measured
and do not attempt to grapple 6ith pro3lems .or 6hich 0uantum mechanics pro/ides no
ans6ers7 At is no more meaning.ul, .or eample, to attempt to calculate the %ath o. an
electron than it is to discuss its colo1r7
Bi3liography and Durther :eading ?#
Thus, 6e can1
<etermine precise /alues o. physical o3ser/a3les 6here the system concerned is in an
eigenstate o. the appropriate operator7
<etermine a mean /alue o. an o3ser/a3le 6here the system is not in an eigenstate o.
the appropriate operator7
<escri3e a system 6hen it is not in an eigenstate in terms o. appropriate superpositions
o. the set o. eigenstates o. the rele/ant operator7
With these theoretical methods, some o. 6hich are illustrated in a discussion o. the
properties o. polarised light in Bo ,7-, 6e can interpret almost all the eperiments 6hich
are o. interest to chemistry7 Where such theoretical methods .ail to gi/e us a 0uantitati/ely
accurate ans6er, as they .re0uently do, it is 3ecause o. the di.Lculties 6hich 6e ha/e in
sol/ing the SchroM dinger eigen/alue2eigen.unction '0uation (,7$7#+, or in e/aluating
the integral in '0uation (,7$72+ in order to determine an epectation /alue, and not
3ecause o. a .ailure o. the 3asic theory7 Dortunately, as 6e shall see in Chapters ? and -,
approimate solutions are .re0uently 0uite su.Lcient .or our purpose7
'1%) 8I85I2RA!HY AN3 6URTHER REA3IN
At is not easy to recommend 3oo4s on 0uantum mechanics, there is a /ery 6ide choice
and many o. the classic tets are no6 /ery old, though their comprehensi/e treatment o.
the su3@ect remains as rele/ant as it e/er 6as7
There are t6o use.ul and comparati/ely recent introductory tets 3y Green1
#7 ;7J7B7 Green, 31ant1m 5echanics I, ".ord =ni/ersity !ress, #$$-7
27 ;7J7B7 Green, 31ant1m 5echanics J, ".ord =ni/ersity !ress, #$$%7
And an additional /olume in the same series7
,7 !7A7 Co, :ntrod1ction to 31ant1m -heory and Atomic Str1ct1re, ".ord =ni/ersity !ress,
#$$57
Cuch more ad/anced 3ut 6ith many ecellent, .ully26or4ed applications is1
*7 :7C7 Golding, A%%lied Wave 5echanics, 8an ;ostrand, London, #$?$7
"ne o. the great classics, not .or the 3eginner is1
57 !7A7C7 <irac, 31ant1m 5echanics, *th edn, ".ord =ni/ersity !ress, #$?-7
;o6 also a/aila3le .rom <o/er !u3lications7
The .ollo6ing three also deser/e the accolade QclassicG7 They are all /ery comprehensi/e tets
particularly aimed at chemists and they pro/ide an in/alua3le source o. re.erence a3out most o.
the 0uantum2mechanical pro3lems and methods o. interest to chemists7
?7 L7 !auling and '7B7 Wilson, :ntrod1ction to 31ant1m 5echanics, CcGra629ill, ;e6 Ror4,
#$,57
?2 The Application o. &uantum Cechanics
-7 97 'yring, J7 Walter and G7'7 >im3all, 31ant1m Chemistry, Wiley, London, #$**7
%7 W7 >auKmann, 31ant1m Chemistry, Academic !ress, London, #$5-7
Core modern 3oo4s 6ith chemists in mind are1
$7 !7W7 At4ins and :7S7 Driedman, 5olec1lar 31ant1m 5echanics, ".ord =ni/ersity !ress,
#$$-7
#07 A7;7 Le/ine, 31ant1m Chemistry, 5th edn, !rentice29all Anc7, ;e6 Jersey, 20007
The .ollo6ing are aimed more at physicists, 3ut all present rather di..erent approaches to the
su3@ect than the preceding /olumes7
##7 L7<7 Landau and '7C7 Li.shitK, 31ant1m 5echanics, 'nglish 2nd edn, !ergamon !ress, ".ord,
#$?*7
#27 J7J7 Sa4urai, 5odern 31ant1m 5echanics, Ben@aminHCummings, Cenlo !ar4, #$%57
#,7 A7S7 <a/ydo/, 31ant1m 5echanics, Addison2Wesley !u3lishing Company Anc7, :eading,
#$?57
#*7 ;7 Nettili, 31ant1m 5echanics Conce%ts and A%%lications, Wiley, Chichester, 200#7
82D '1% T$e sine< #osine an/ exponential ";n#tions
We ma4e .re0uent use o. the sine, cosine and eponential .unctions, and their deri/a2
ti/es, in this chapter7 The particular results 6hich 6e re0uire can 3e readily deri/ed
i. 6e recall that each o. these .unctions can 3e epressed as a po6er series1
sin!ax " = ax !ax "
,
,,U + !ax "
5
,5U !ax "
-
,-U +

cos!ax " = # !ax "


2
,2U + !ax "
*
,*U !ax "
?
,?U +

ep!ax " e
ax
= # + ax + !ax "
2
,2U + !ax "
,
,,U + !ax "
*
,*U +
ep!ax " e

ax
= # ax + !ax "
2
,2U !ax "
,
,,U + !ax "
*
,*U +

nU = n!n #"!n 2"!n ," # is called factorial nP e7g7 5U = 5 * , 2 # =


#207
<i..erentiating sin!ax" term23y2term 6ith respect to x 6e ha/e1
d Zsin!ax "\,dx = a ,a !ax "
2
,,U + 5a !ax "
*
,5U -a !ax "
?
,-U +
= aZ# !ax "
2
,2U + !ax "
*
,*U !ax "
?
,?U + \ = a cos!ax "
Similarly
and
d Zcos!ax "\,dx = a sin!ax "
d Zep!ax "\,dx = a ep!ax "
d Zep!ax "\,dx = a ep!ax "
G
2
0
82D '1& T$e Normalisation an/ ort$ogonalit0 o" eigen";n#tions
Normalisation
The s0uare o. an eigen.unction (G + e/aluated at any point in space gi/es the pro32
a3ility that the particle descri3ed 3y that eigen.unction 6ill 3e .ound at that point7
Since the pro3a3ility o. Lnding the particle some6here 6ithin the 6hole o. the region
o. space in 6hich it is allo6ed to mo/e must 3e one (certainty+, it .ollo6s that the
sum o. the /alues o. G
2
e/aluated at e/ery point in space must 3e one .or a physi2
cally accepta3le eigen.unction7 This re0uirement is represented mathematically 3y an
integration o/er all space1

all space
G
2
dv = #.0
We can illustrate the normalisation process using the eigen.unctions 6hich 6e
ha/e .ound .or the electron conLned to a ring7 Dor the cosine .unctions .or eample1
G
ca
= N cos!a$"
Where a = 0 # 2 . . . and N is the normalising constant 6hich 6e ha/e to Lnd7
An this particular pro3lem the Q6hole o. spaceG, as .ar as the electron is concerned, is
a complete circuit o. the ring, i7e7 all /alues o. $ .rom 0 to 2( 7
Dor the special case 6here a = 0 cos!a$" = #.0 and 6e ha/e1
2(

2
ca
d$
=
N
0
2(
# d$ = N
0
2
Z$\
2(
= 2(N
2
There.ore, .or a normalised eigen.unction 6e must ha/e N = #,

2( 7 We al6ays
ta4e the positi/e sign, 3ut the choice o. sign can ha/e no e..ect upon the calculation
o. any property 6hich 6e can measure7
When a is not Kero 6e ha/e1
2(

G
2
2(
2

2
2(
N
2

ca
d$
=
N
0
{cos!a$"}
0
d$ =
2
{
#
+
cos!2a$"
}
d$
0
N
2

=
2
$
+
sin!2a$"

2(
2a
0
=
N
2
2
2

2(
=
N (
Thus, .or these .unctions N = #,

( and the correctly normalised eigen.unctions


are 6ritten1
#
G
ca
=
(
cos!a$"
The sine .unctions can 3e normalised in the same 6ay and the normalising constant
is .ound to 3e

!#,( " .or these also7


2rt$ogonalit0
The eigen.unctions 6hich sol/e SchroM dingerGs e0uation also ha/e the property
o. orthogonality, i7e7 6hen the product o. t6o di..erent eigen.unctions is
integrated
2
2
0
0
Qo/er all spaceG the result is Kero7 Thus, .or t6o cosine eigen.unctions1
2(
#

(
cos!a$"

cos!*$" d$
=
0 i. a
=
*
0
This is a /ery important property 6hich epresses the .act that any one eigen.unc2
tion cannot 3e 6ritten in terms o. the other eigen.unctions o. the same SchroM
dinger operator7 This is eactly the same as saying that a coordinate on the x2
ais o. a graph cannot 3e epressed in terms o. a co2ordinate, or co2ordinates, on
the y2ais o. the same graph7 This is 3ecause the t6o aes are orthogonal, 6hich
is another 6ay o. saying that they are at right angles to each other7 We can
demonstrate the orthogonality o. t6o cosine .unctions simply 3y carrying out the
re0uired integration1
2(
#

(
cos!a$"

cos!*$" d$
=
0
2(
#

(
{
cos!Za
+
*\$"
+
cos!Za

*\$"
}
d$
0
#

sin
{
!a
+
*"$
}
sin
{
!a

*"$
}

2(
=
( !a + *"
+
!a *"
0
=
Both terms are Kero at $ = 0 and 2( 3ecause a and * are integers7
82D '1' Normalisation an/ ort$ogonalit0 o" t$e eigen";n#tions "or an ele#tron in a
linear ?ox
Normalisation (See also Bo ,72+
The normalisation integral is1
L
{N sin!n( x,L"}
0
dx = #.0
3ut sin
2
# =
#
!# cos 2#" and the integral can there.ore 3e 6ritten as1
L
N
2

N
2

L

L
2
{
#

cos!2n( x,L"
}
dx
=
2
0
N
2
x

2n(

sin!2n( x,L"
since sin!2n( " = sin!0" = 07
=
2
!L

0

0

0"

There.ore, N
2
L,2 = # or N
2
= L,2 and N = !2,L"7
We may ta4e either sign .or the s0uare root since the phase o. the 6a/e .unction
has no e..ect upon any 0uantity 6hich 6e can measure7
e
2rt$ogonalit0 (See also Bo ,72+
The 6a/e .unctions corresponding to t6o di..erent /alues o. the 0uantum num3er, n,
are orthogonal, i7e7 the integral o. their product o/er the length o. the 3o is Kero7
We can pro/e this 3y integrating the product o. t6o 6a/e .unctions ha/ing 0uantum
num3ers n and m 6ith normalising constants N and 5 respecti/ely1
L
2 N5

L
sin!n( x,L"

sin!m( x,L" dx
0
L
N5

(x

(x

=
L
cos
0
Zn

m\
L
cos
Zn
+
m\
L
dx
N5

sin!Zn

m\( x,L"
sin!Zn
+
m\( x,L"

L
=
L Zn m\(,L

Zn + m\(,L
0
= 0 3ecause n and m are integers.
82D '1( Ele#troni# spe#tra o" #onH;gate/ pol0enes
According to the theory o. the chemical 3onding in con@ugated polyenes (Chapter ?+,
the ( 2electrons o. these molecules occupy or3itals 6hich are delocalised o/er the
6hole o. the car3on2atom chain7 These electrons should there.ore 3eha/e rather li4e
electrons in a linear 3o and, in particular, the electron2in2a23o model should pro/ide
approimate /alues .or their energy le/els7 There is no dou3t that the a3sorption 3and
o. longest 6a/elength, 6hich mo/es into the /isi3le spectral region as the length o.
the chain increases, is due to an electronic transition .rom the highest occupied to
the lo6est unoccupied ( 2electron energy le/el and the energy o. this 3and has 3een
correlated 6ith the gap 3et6een these energy le/els in many 0uantum2mechanical
treatments o. polyene spectra7 (See, .or eample, S7D7 Cason, 31arterly Revie0s of
the Chemical Society, %), 2%-, #$?#7+ Theory and eperiment may 3e related in the
.ollo6ing manner7
Consider a cyanine, a linear polyene, 6hich has the general .ormula sho6n in
Digure B,7*7#7 There are 2; + 2 3onds in the con@ugated system 3et6een the t6o
nitrogen atoms, 3ut it is 6ell 4no6n that methyl groups etend the con@ugated system7
We there.ore allo6 .or this (hypercon@ugati/e+ e..ect 3y adding one 3ond .or each o.
the t6o 9
,
CI;IC9
,
groups gi/ing a total o. 2; + * 3onds in the con@ugated system7
The length, L, o. the con@ugated system can no6 3e 6ritten as !2; + *"l, 6here l
is the mean 3ond length7 'ach car3on atom contri3utes one ( 2electron and the t6o
nitrogen atoms contri3ute three 3et6een them (# .rom ;+, 2 .rom ;1+, so that 6e
ha/e a total o. 2; + *( 2electrons7
The energy le/els o. an electron in a 3o are gi/en 3y the .ormula1
n
2
h
2
E
n
=
%m L
2
!n
=
# 2 , . . ."
;
9
,
C
77
+
C9
,
9
,
C
; (IC9 C9 +
;
C9 ;
C9
,
9
,
C
9
,
C
+



C9 ( C9
77
C9
,
C9 +
;
;
C9
,
6ig;re 8'1(1% The resonance structures o. cyanine dyes
Since the electrons occupy the energy le/els in pairs, the 0uantum num3er (n
hol
+
o. the highest occupied le/el is !2; + *",2 = ; + 2 and the 0uantum num3er o. the
lo6est unoccupied le/el, n
lul
, is ; + 2 + # = ; + ,7 Thus, using the a3o/e .ormula the
energy di..erence ( E+ 3et6een the lo6est unoccupied and highest occupied le/els is1
E = E
lul
E
hol
=
{
!; + ,"
2
!; + 2"
2
}h
2
%m
e
!2;
+
*"
2
l
2
!2; + 5"h
2
=
%m
e
!2;
+
*"
2
l
2
and 6e there.ore epect that a graph o. E against !2; + 5",!2; + *"
2
6ill 3e a
straight line o. gradient h
2
,%m
e
l
2
7 To calculate the gradient 6e re0uire an estimate
o. the mean 3ond length (l+7 Because o. the resonance 3et6een the t6o cyanine
tautomers, there is no 3ond alternation as in the polyenes and all the CIC 3onds
are e0ual in length7 There are /ery .e6 hydrocar3ons .or 6hich this is the case,
3ut 3enKene is one such 6hich suggests that 6e set l
=
#.,$

#0

#0
m, so that the
theoretical gradient is1
h
2
!?.?2? #0

,*
"
2
,#2

#0

20
J
%m
e
l
2
=
% $.#0$ #0

,#
!#.,$ #0

#0
"
2
=
Dor comparison 6ith eperiment 6e use the data .or the cyanines ta4en .rom
CasonGs re/ie6 and gi/en in Ta3le B,7*7#7 The data are plotted in Digure B,7*727
The eperimental slope o. ,#,

#0

20
J is in remar4a3le agreement 6ith the
simple model o. the electron in a 3o7 But it must 3e noted that .or other polyenes,
6here all CIC 3onds are either .ormal dou3le 3onds, C
=
C, or .ormal single 3onds,
CIC, the resulting alternation o. 3ond length and the conse0uent alternation o. the
electric Leld o. the ' 2electrons, in 6hich the ( 2electrons mo/e, ma4es the simple
theory less applica3le7 These additional e..ects are discussed 3y Cason7 ;e/ertheless,
this eample sho6s that e/en the most simple 0uantum2mechanical model is capa3le
Ta?le 8'1(1% The electronic spectra o. the cyanines
;
#
!2; + 5",!2; + *"
2
07#$**
<
ma
,nm
,#275
E,J #0

20
?,755
2 07#*0? *#?70 *-7-*
, 07##00 5#$70 ,%72?
* 070$0, ?2570 ,#7-%
5 070-?5 -,*75 2-70*
? 070??* %*%70 2,7*2

'

(
J


#
0

2
0
+
%0
-0
?0
50
*0
,0
20
#0
0
0700 0705 07#0 07#5 0720 0725
(2; + 5+H(2; + *+
2
6ig;re 8'1(1& E vers1s chain2length parameter .or cyanine dyes
o. gi/ing a 0uantitati/e interpretation o. real chemical data and there3y enhancing
our understanding o. the .undamental properties o. con@ugated molecules7
82D '1) Cal#;lation o" t$e expe#tation Aal;e o" t$e ang;lar moment;m o"
an ele#tron on a ring
We consider the electron in the state ha/ing the 6a/e .unction1
#
G
a
=
(
cos!a$"
6hich is not an eigen.unction o. the angular momentum operator, ih` D,D $7
The
epectation /alue o. the angular momentum, l, .or this eigen.unction is calculated as
.ollo6s1
2(

# ih
`
D

#
l
=
(
cos!a$"
0
2(

D$

(
cos!a$" d$
ih
`

=
(
0
cos!a$"
D
cos!a$" d$
D$
2
iah` =
(
iah
`
2(
cos!a$" sin!a$" d$
0
2(

iah` #
2(
=
2(
0
sin!2a$" d$ =
2(

2a
Zcos!2a$"\
0
=
0.
Bearing in mind (Appendi %+ the .act that1
cos!ax" =
#
{ep!+iax" + ep!iax"}
6e see that the cosine .unction is a sum o. the t6o angular momentum eigen.unctions,
ep!+iax" and ep!iax"7 Thus, i. 6e measured the angular momentum o. the system
6e 6ould epect to Lnd /alues o. +ah` and
ah`
in e0ual num3ers 6hich 6ould lead
to a mean /alue o. Kero as the num3er o. measurements increased7
82D '1* Heisen?erg ;n#ertaint0 relations$ips
The 3est 4no6n o. these, and the most important as .ar as chemistry is concerned,
are those in/ol/ing momentum and position along the same coordinate1
%
x
x h,*( %
y
y h,*( %
B
B h,*(
and those in/ol/ing t6o components o. angular momentum, i7e71
l
x
l
y
h,*( l
y
l
B
h,*( l
B
l
x
h,*(
An these relationships it is assumed that there is a Gaussian distri3ution o. the
uncertainties, i7e7 p is the root2mean2s0uare o. the )p o. the indi/idual measurements1

% =

!)%
i
"
2
i
As 6e ha/e seen in this chapter, the uncertainty relationships are intimately related
to the non2commutation o. the operators in/ol/ed7 An the case o. the angular momen2
tum operators, this is epressed in the .ollo6ing use.ul e0ualities deri/ed in Bo *7#1
Zl

x
l

y
\ = ih` l

B
P Zl

y
l

B
\ = ih` l

x
P Zl

B
l

x
\ = ih` l

y
6here Za *\ a * * a7
There is also an uncertainty relationship 6hich connects energy and time1
E t
h,*(
At is /ery /alua3le and 6e use it in Chapter %7 9o6e/er, it must 3e clearly under2
stood that, since time is not an o3ser/a3le, the relationship has an origin and signiL2
cance 0uite di..erent .rom the others 0uoted here7 The distinction is discussed in more
ad/anced tets, e7g7 J7J7 Sa4urai, 5odern 31ant1m 5echanics, Ben@aminHCummings,
Cenlo !ar4, #$%57
There is a /ery good discussion o. the 9eisen3erg uncertainty principle in C7
Born, Atomic Physics, Blac4ie & Son, ,rd 'dn, London #$**, Appendi FFAA7
82D '1+ !olarise/ lig$t an/ @;ant;m me#$ani#s
We can use 6ell24no6n results .rom classical optics to illustrate se/eral o. those
aspects o. 0uantum mechanics 6hich appear puKKling 6hen 6e Lrst encounter them7
The eperiments and their interpretation ha/e 3een discussed 3y <irac in Q-he Princi+
%les of 31ant1m 5echanicsG7 The Lrst edition o. this .amous 3oo4 appeared in #$,0
and 6as one o. the most important contri3utions to the mathematical and philosophical
.oundations o. 0uantum mechanics7 The eperiments in 0uestions are the .ollo6ing7
(See Chapter % .or .urther in.ormation a3out polarised light7+
A 3eam o. light propagating in the B direction and polarised in the xB plane is
directed onto a polariser7 The latter is an optical de/ice 6hich transmits incident light
i. the light is polarised along a particular direction 6hich 6e here call t t

, 3ut
6hich a3sor3s all the incident light i. it is polarised along a a

, the direction at
right angles to t t

(Digure B,7-7#+7 We assume the polariser to 3e per.ect7
Both a a

and t t

are perpendicular to the direction o. propagation o. the
light7 When the incident light is polarised at some intermediate angle, K , to t t
,
eperiment sho6s that i. :
0
is the intensity o. the incident polarised light and :
t
the
intensity o. the transmitted light then1
:
t
= :
0
cos
2
K and :
a
= :
0
sin
2
K
6here :
a
= :
0
:
t
, the intensity o. the light lost 3y a3sorption7 The transmitted light
is also polarised 3ut along t t

and not along its original direction o. polarisation
at an angle o. K to t t

7
=sing a techni0ue 4no6n as photon counting, the eperiments descri3ed a3o/e
can 3e carried out 6ith a 3eam o. light o. such a lo6 intensity that the photons
passing through the polariser can 3e indi/idually recorded7 Dor light polarised along
t

t

e/ery photon is transmitted 6hile .or light polarised along a

a

e/ery photon
is a3sor3ed and this presents us 6ith little conceptual di.Lculty7 But 6hat o. the
eperiments 6ith light polarised at an angle o. K to t t

J A. 6e no6 consider the
.ate o. each indi/idual photon 6e are una3le to say deLnitely 6hether it 6ill 3e
transmitted or a3sor3ed 3y the polariser7 We can only say that there is a pro3a3ility
o. cos
2
K that it 6ill 3e transmitted and a pro3a3ility o. sin
2
K that it 6ill 3e a3sor3ed
t
3
a
t
6ig;re 8'1+1% !lane o. polarisation o. incident light 6ith respect to directions o. transmission,
t

t

, and a3sorption, a

a

since this 6ill gi/e us the 4no6n eperimental result i. a large num3er o. photons
are su3@ected to the polarisation test7 We Lnd that 6e can only ma4e statements a3out
pro3a3ilities in respect o. the results o. a measurement on a single particle 6hich
o3eys the la6s o. 0uantum mechanics7 Thus, the Lrst aspect o. 0uantum mechanics
illustrated 3y the a3o/e eample is the statistical nature o. our 4no6ledge concerning
the 3eha/iour o. indi/idual particles and the results o. indi/idual measurements7
The second important point 6hich emerges a3o/e is that the ma4ing o. the mea2
surement has a pro.ound inOuence upon the particle su3@ected to that measurement7
The eperimental result is that all the photons 6hich pass through the polariser are
polarised along t

t

6hereas those 6hich are a3sor3ed must 3e polarised along
a

a

7 But all the incident photons 6ere polarised at an angle o. K to t

t

so
that the polarisation o. e/ery photon su3@ected to measurement has 3een changed7
There.ore, i. 6e ma4e a .urther measurement on the photons 6hich pass through the
polariser the o3@ects o. the second measurement are not eactly the same as the o3@ects
o. the Lrst measurement, their o3ser/a3le property o. polarisation has 3een changed7
The photons ha/e 3een Q.orcedG into eigenstates o. the operator 3y the measurement
process7 An general, there is no such thing as an eperimental measurement 6hich has
no e..ect upon the system measured, though there 6ould 3e no apparent e..ect i. each
incident photon 6as polarised along t

t

7
The concept o. polarisation as an o3ser/a3le property leads us to as4 6hat the
corresponding operator, eigen/alues and eigen.unctions are7 There are t6o eigenstates
o. polarisation in the a3o/e eperiment7 A. a photon is in eigenstate G
t
then it is
transmitted 3y the polariser, i. it is in the eigenstate G
a
then it is a3sor3ed7 A. 6e call
the Qpolarisation analysingG operator A

then1
A

G
t
= # G
t
and A

G
a
= 0 G
a
and .or a 3eam o. light polarised along t t

e/ery measurement gi/es the same
result1 photon transmitted7 Dor light polarised along a a

6e al6ays get the result1
photon a3sor3ed and annihilated7
A. 6e no6 consider the case o. photons polarised at an angle o. K to t

t

then, according to 0uantum mechanical principles, this state o. polarisation may 3e
descri3ed as a linear com3ination o. the possi3le eigenstates o. polarisation, i7e71
G
K
= C
t
G
t
+ C
a
G
a
6here the coe.Lcients C
t
and C
a
gi/e the contri3utions o. each o. the t6o eigenstates
to the state G
K
7 The coe.Lcients must 3e normalised so that1
C
t
2
+ C
a
2
= #.0 !B,.-.#"
3ecause the 6a/e .unction G
K
descri3es a single photon and the total pro3a3ility o. it
3eing either a3sor3ed or transmitted must 3e #707 Durthermore, and again according to
0uantum2mechanical principles, the outcome o. the determination o. the polarisation
o. a photon in the state G
K
must 3e such that the pro3a3ility that the photon is
polarised along t t

and is transmitted is C
t
2
and the pro3a3ility that the photon is
polarised along a a

and is a3sor3ed is C
a
2
7 But 6e 4no6 these pro3a3ilities .rom
eperiment to 3e cos
2
K and sin
2
K respecti/ely, so that1
C
t
= cos K and C
a
= sin K
!ro3lems .or Chapter , -#
and the .act that sin
2
K + cos
2
K = #.0 is eactly 6hat is re0uired to satis.y the nor2
malisation condition '0uation (B,7-7#+7 This last point illustrates ho6 the concepts
o. the superposition o. states and epectation /alue allo6 us to etract use.ul in.or2
mation .rom measurements on systems 6hich are not, at the time immediately 3e.ore
the measurement, in eigenstates o. the operator corresponding to the o3ser/a3le prop2
erty 6hich 6e are measuring7 At also sho6s that eigen.unctions (eigenstates+ and
eigen/alues are .undamental 3ut not immuta3le thingsP they are determined 3y the
measurements 6hich 6e choose to ma4e7 A. 6e rotated the polariser 3y
o
then a ne6
pair o. eigenstates 6ould 3e appropriate .or a discussion o. the eperiment a3o/e7
!R285EMS 62R CHA!TER '
#7 ConLrm the entries in columns three and .our o. the .ollo6ing ta3le7
"perator, P

D
2
Dunction, As an eigen.unction
o. P

J
A. QyesG, 6hat is
the eigen/alueJ
D#
2
D
D#

D
Dx
+
L

xD
sin # yes #
sin
2
# no
ep(ax+ yes a + L
2
Dx
+
L x yes 2 + L

xD
yD

Dx
+
Dy

D D

xy yes 2
xy
Dx
+
Dy
xy no
27 Sho6 that the .unctions ep!+inx" and ep!inx" are eigen.unctions o. the energy
operator .or an electron in a linear 3o, each ha/ing the same eigen/alue o. n
2
h`
2
,2m
e
7
,7 A deeper understanding o. the .ollo6ing pro3lem should 3e possi3le a.ter Chapters *
and 5 ha/e 3een studied7 But no 4no6ledge o. the material co/ered there is re0uired
to complete the present eercise7
The .ollo6ing, normalised .unctions are .unctions o. the polar coordinate, # , only,
apart .rom G
s
6hich is simply a constant1
G
s
=

!#,2" G
d
=

!5,%"!, cos
2
# #"
G
%
=

!,,2" cos # G
f
=

!-,%"!5 cos
,
# , cos #"
-2 The Application o. &uantum Cechanics
#
#
Sho6 that these .unctions are eigen.unctions o. the angular momentum operator L
2
1
L

2 2 2
#
=
cot #

D,D #
+
D ,D #
The eigen/alues o. L
2
gi/e the s0uare o. the or3ital angular momentum in
units o. !h,2( "
2
7 Sho6 that the eigen/alues are l!l + #", 6here l = 0, #, 2 and
, .or s % d and f respecti/ely7
*7 The .unctions
a
= N
a

x!L x" and


*
= N
*
x!L x", 6here N
a
and N
*
are nor2
malising constants, are not eigen.unctions .or the electron in a one2dimensional 3o
o. length L, 3ut they do satis.y the 3oundary conditions o. that system7
a+ Sho6 that N
a
= 2

,,L
2
, N
*
=

!,0,L
5
" and that the .unctions are not ortho2
gonal7
3+ =sing the position operator (Section ,7#,7#+ and the epression .or an epectation
/alue ('0uation (,7$72++ calculate the epectation /alue o. x, x, .or 3oth 6a/e
.unctions,
a
and
*
7 S4etch graphs o. the t6o .unctions Zset L
=
#.0\ to eplain
the di..erence in the t6o /alues o. x 7
c+ Sho6 that !
*
|x|
*
"
2
=
*
|x
2
|
*
7 This is e0ui/alent to saying that the s0uare
o. the mean o. a set o. num3ers is not e0ual to the mean o. the s0uares o. those
num3ers7
57 Calculate the epectation /alue .or the energy, E
*
, using the .unction
*
.rom 0uestion
*, the 4inetic energy operator ('0uation (,7?72++ and the epression .or an epectation
/alue ('0uation (,7$72++7 Write do6n the lo6est eact energy eigen/alue, E
#
, .or the
electron2in2a23o pro3lem ('0uation (,7?75++ and sho6 that E
*
= #.0#,2E
#
7 The .act
that the epectation energy calculated 6ith the approimate 6a/e .unction is greater
than the eact lo6est energy is an eample o. the /ariation theorem (Appendi 2+7
Note1 Be care.ul to distinguish 3et6een h and h`
= h,2( P '0uation (,7?75+ uses
the
.ormer and '0uation (,7?72+ the latter7
?7 =se '0uation (,7,7?+ to dra6 0uantitati/e energy2le/el schemes .or the ( 2electrons o.
3enKene (C
?
9
?
+, naphthalene (C
#0
9
%
+ and anthracene(C
#*
9
#0
+7 'stimate the radius
o.
the ring 3y assuming that its circum.erence is the num3er o. peripheral CIC 3onds
#,$ pm7 !lace the a/aila3le electrons in the lo6er energy le/els o. your energy2le/el
schemes and calculate the energy re0uired .or a transition .rom the highest occupied
to the lo6est unoccupied le/el .or each molecule7 Compare your results 6ith the
eperimental data .or the %ara23and 6hich is .ound in the electronic spectra o. these
molecules at $755, ?7%- and 5.2*

#0

#$
J .or 3enKene, naphthalene and anthracene
respecti/ely7
The agreement o. theory and eperiment is good, considering the simplicity o. the
model7 Among the most important aspects o. the pro3lem 6hich 6e ha/e neglected are
the e..ects o. the 3onds across the ring in naphthalene and anthracene and the strong
conLguration interaction (see Chapter ##+ 3et6een the .our possi3le ecited states o.
the same energy7
Chapter *
Ang;lar Moment;m
*70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -,
*7# Angular momentum in classical mechanics . . . . . . . . . . . . . . . . . . . . . . -,
*72 The conser/ation o. angular momentum . . . . . . . . . . . . . . . . . . . . . . . . -5
*7, Angular momentum as a /ector 0uantity . . . . . . . . . . . . . . . . . . . . . . . -5
*7* "r3ital angular momentum in 0uantum mechanics . . . . . . . . . . . . . . . . . -?
*7*7# The /ector model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . --
*75 Spin angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -%
*7? Total angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
*7?7# The addition and conser/ation o. angular momentum in 0uantum
-%
mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -$
*7?72 The la6s o. 0uantum2mechanical angular momentum . . . . . . . . . . %#
*7- Angular momentum operators and eigen.unctions . . . . . . . . . . . . . . . . . %2
*7-7# The raising and lo6ering, shi.t or ladder operators . . . . . . . . . . . . %2
*7% ;otation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %,
*7$ Some eamples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %*
*7#0 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . %?
!ro3lems .or Chapter * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $,
(1. INTR23UCTI2N
An the application o. the 0uantum theory to chemistry, angular momentum is argua3ly
as important as energy7 At plays a /ital part in spectroscopy and in the theory o. atomic
structure7 At has e/en 3een suggested that angular momentum plays a more important
role than energy in determining the outcome o. intermolecular collisions7
#
Be.ore con2
sidering the 0uantum theory o. angular momentum 6e shall descri3e the phenomenon in
classical terms7
(1% ANU5AR M2MENTUM IN C5ASSICA5 MECHANICS
Consider a mass (&+ mo/ing 6ith /elocity (v+ in a circular path (radius r+ (Digure *7#+7
At any moment in time the /elocity o. the 3ody is directed at right angles to a line @oining
the 3ody to the centre o. the circle7 By deLnition, the linear momentum (p+ o. the 3ody
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
-* Angular Comentum
m
0
r
"
6ig;re (1% Angular momentum generated 3y an or3iting mass, m
is the product o. the mass and the /elocity1
p = & v !*.#.#"
and the angular momentum (a+ is the /ector product o. p and r,1
a = r p = rp sin # = r& v !*.#.2"
6here # is the angle 3et6een r and p7 The 0uantities in 3old type, r, v, p and a are all
/ector 0uantities, i7e7 they ha/e 3oth magnitude and direction7 The /ector a is located
at the centre o. the circle a3out 6hich the mass m rotates and, 3ecause it is the /ector
product o. r and p, its direction is at right angles to the plane containing r and p7 An
order to deLne a positi/e and negati/e direction .or a 6e Lrst deLne a right2handed co2
ordinate system (Digure *72+, 6hich is one 6here a rotation .rom +x to +y ad/ances a
right2handed scre6 along the positi/e direction o. the B2ais7 Then, i. v is directed .rom
+x to6ards +y the resulting angular momentum is positi/e, 6hereas i. the direction o.
motion is .rom +y to +x a is negati/e7 Thus, 3y rotating a 6heel on an ale 6e can
generate either positi/e or negati/e angular momentum, depending upon the direction
o. rotation7 The angular momentum so generated is represented 3y a /ector 6hich lies
along the ale7 A. the rotating 6heel is /ie6ed .rom +K, cloc46ise (Digure *7,(a++ and
N
R
F
An a right2handed co2ordinate system, a rotation
.rom +F to +R ad/ances a right2handed scre6
in the positi/e N2direction
6ig;re (1& <eLnition o. a right2handed co2ordinate system
Angular Comentum as a 8ector &uantity -5
N
N
a
p = m p M m
a
(a+ (3+
6ig;re (1' Angular momenta produced 3y cloc46ise and counter2cloc46ise rotations
counter2cloc46ise (Digure *7,(3++ rotations produce negati/e (a directed a6ay .rom the
o3ser/er+ and positi/e (a directed to6ards the o3ser/er+ angular momentum respecti/ely7
(1& THE C2NSERVATI2N 26 ANU5AR M2MENTUM
Li4e energy, angular momentum is a conser/ed 0uantity and, 3eing a /ector 0uantity, 3oth
the magnitude and direction o. a are maintained i. they are not inOuenced 3y eternal
.actors7 The constancy o. direction is eploited in the gyroscope 6hich, prior to satellite
technology, 6as 6idely used in na/igational e0uipment7 At is the property 6hich 4eeps
a spinning top upright and is surprisingly strong7 Ta4e a cycle 6heel, hold the spindle,
one end in each hand, and start the 6heel rotating gently7 ;o6 mo/e the 6heel /ertically
up and do6n or horiKontally .rom side to side7 Rou should .eel no resistance to these
mo/ements since you are not attempting to change the direction o. the angular momentum
/ector7 ;o6 try to tip the 6heel 3y raising one hand and lo6ering the otherP the resistance
to this mo/ement arises 3ecause the direction o. the angular momentum is conser/ed7 A.
you do this 6hile seated on a s6i/elling o.Lce chair you 6ill Lnd that the angular
momentum is conser/ed 3y a rotation o. the chair7
The conser/ation o. angular momentum ma4es the spinning 3ullets .rom a gun 6ith a
riOed 3arrel much more sta3le in Oight than those .rom a smooth23ored 6eapon, greatly
increasing the range o. accuracy and hence lethality7 The introduction, 3y the =nion,
o. the SpringLeld riOed23ore mus4et into the American Ci/il War (#%?# I #%?5+
caused the Con.ederacy dread.ul losses 3e.ore they adopted ne6 tactics and o3tained
similar 6eapons themsel/es7 This e..ect on pro@ectiles 6as 4no6n to the ancient
Gree4s 6ho, around 500 BC, used 6ooden @a/elins 6ith a length o. string 6ound
around the centre in athletic competitions7 When the @a/elin 6as thro6n the athlete
6ould hold on to the string, causing the @a/elin to rotate there3y increasing the length
o. his thro67
(1' ANU5AR M2MENTUM AS A VECT2R QUANTITY
Since it is a /ector 0uantity, angular momentum has a component in any direction in
space 6hich 6e choose to speci.y7 At is use.ul to 3e a3le to speci.y the components along
the x, y and B aes o. a Cartesian co2ordinate system and this can 3e easily done7 A. 6e
-? Angular Comentum
2(
4no6 the angles L, K and N 3et6een the angular momentum /ector (a+ and the x, y, and
B aes respecti/ely, then the re0uired e0uations are1
a
x
= a cos L a
y
= a cos K a
B
= a cos N (*7,7#+
The classical angular momentum 6hich has 3een descri3ed a3o/e is also called or3ital
angular momentum since it arises as a result o. a mass eecuting an or3it around a
Led point7
(1( 2R8ITA5 ANU5AR M2MENTUM IN QUANTUM MECHANICS
"r3ital angular momentum is also .ound in 0uantum mechanics (Bo *7#+ 3ut the 0uantum
and classical or3ital angular momenta di..er in t6o aspects related to 0uantisation7 Dirstly,
in 0uantum mechanics the total angular momentum is 0uantised 6ith possi3le magnitudes
gi/en 3y the e0uation1
a =

d!d + #"
h


d!d + #"
h`
!*.*.#"
6here h is !lanc4Gs constant and d is a 0uantum num3er 6hich can ta4e all positi/e
integer /alues, including Kero, i7e7 d = 0 # 2 , . . . A molecule rotating .reely in space
has angular momentum o. this type7 ;ote that the 0uantity h,2( occurs so .re0uently and
is so important that it has its o6n sym3ol (h` + 6hich is spo4en Qh2crossG7
Secondly, though the x, y and B components o. a classical angular momentum /ector
can al6ays 3e speciLed as in '0uation (*7,7#+, 0uantum mechanics places /ery important
restrictions on the components o. angular momentum 6hich can 3e speciLed7 The Lrst o.
these restrictions is that the component in only one direction in space may 3e speciLed7
Thus, i. the B component is gi/en, no or y components may 3e speciLed7 Durthermore,
the components in the direction 6hich can 3e speciLed, and there is no restriction in
our choice o. this one direction, are 0uantised7 Whiche/er the direction chosen, B in
'0uation (*7*72+, the allo6ed 0uantised components are gi/en 3y the e0uation1
a
B
= m
d
h,2( m
d
h`
!*.*.2"
6here m
d
is a 0uantum num3er 6hich can ta4e all integer /alues .rom d to +d 1
m
d
= d !d #" !d 2" . . . # 0 +# . . . + !d #" +d (*7*7,+
gi/ing 2d + # /alues .or m
d
7 The results epressed in '0uations (*7*7#+, (*7*72+ and (*7*7,+
are deduced .rom the angular momentum commutation relationships in Bo *7#7
Thus, .or d = 0 m
d
= 0
d = # m
d
=
# 0
+
#
d = 2 m
d
=
2

# 0
+
#
+
2 etc7
An '0uation (*7*72+, the B ais has 3een selected as the one .or 6hich the components
o. angular momentum are speciLed7 This is purely a matter o. choice 3ut it is a con/ention
6hich has 3een uni/ersally adopted7 The sym3ol, m
d
, .or the 0uantum num3er a3o/e 6as
chosen 3ecause o. the close relationship 3et6een this 0uantum num3er and the magnetic
properties o. atoms7 The origins o. this relationship 6ill 3e descri3ed in Chapter #27
"r3ital Angular Comentum in &uantum Cechanics --
O
m
d
= +2
m
d
= +#
m
d
= 0
m
d
= #
m
d
= 2
0 = ,57,
0 = ?57$
0 = $070
0 = ##*7#
0 = #**7-
6ig;re (1( The L/e B2components o. an angular momentum characterised 3y an angular momen2
tum 0uantum num3er o. 2
Thus, in 0uantum mechanics, or3ital angular momentum is descri3ed 3y t6o 0uantum
num3ers, d 6hich gi/es the /alue o. the 0uantised total angular momentum through
'0uation (*7*7#+ and m
d
6hich gi/es the allo6ed components o. the angular momentum in
the B direction through '0uation (*7*72+ and is restricted in its /alues 3y '0uation (*7*7,+7
This .orm o. 0uantisation is 4no6n as space 0uantisation 3ecause the spatial orientation o.
the angular momentum 6ith respect to the B2ais is restricted 3y the 0uantisation o. its B
component7 ;ote that the maimum component, a
B
is d
h`
and is there.ore al6ays smaller
than the total angular momentum,

Zd!d + #"\h
`
7 This means that the 0uantised component
(a
B
+ ne/er lies eactly along the total angular momentum /ector (a+ (Digure *7*+7 This is
a .urther conse0uence o. the uncertainty principle7 A. a
B
6ere aligned along a 6e 6ould
4no6 not only the /alues o. a and a
B
, 3ut also those o. a
x
and a
y
, 3ecause they 6ould
3oth 3e Kero7 Thus, 6e 6ould 4no6 e/erything that there is to 4no6 a3out the angular
momentum o. the system and in 0uantum mechanics that is not permitted, as 6e ha/e
seen in Section ,7#07 Digure *7* illustrates this point7
(1(1% T$e Ae#tor mo/el
We ha/e a situation in 6hich the length o. a /ector and its pro@ection on the B ais are
deLned, 3ut nothing more a3out its orientation can 3e said7 Since there is no reason to
treat the and y aes di..erently, 6e must assume that the pro@ection o. the /ector in
the y2plane points in all possi3le directions 6ith e0ual pro3a3ility7 This concept .orms
the 3asis o. the vector model o. angular momentum in 6hich the /ector d is en/isaged
as precessing a3out the B ais so that it descri3es a cone a3out that ais in 6hich the
hal.2angle at the ape o. the cone (# + is gi/en 3y '0uation (*7*7*+1
m
d
cos #
=
d!d
!*.*.*"
+ #"
We should not lea/e this aspect o. angular momentum 6ithout ta4ing ad/antage o.
the opportunity it pro/ides o. illustrating the 6ay in 6hich classical mechanics may
3e regarded as a limiting case o. 0uantum mechanics7 The .act that there is al6ays a
Lnite angle (# + 3et6een the total 0uantum2mechanical angular momentum /ector and its
-% Angular Comentum
=
maimum B component is a non2classical result7 Since the maimum /alue o. m
d
is d ,
cos(# Zmin\+ is gi/en 3y1
m
d
Zma\ d

d
cos!# Zmin\"
=
d!d
+ #"
=
d!d + #"
=
d + #
(*7*75+
Thus, as d 3ecomes /ery large cos!# Zmin\" tends to #, # Zmin\ tends to Kero and
the maimum possi3le B component o. the angular momentum approaches the /alue o.
the total angular momentum, 6hich is 6hat it 6ould 3e in classical mechanics7
(1) S!IN ANU5AR M2MENTUM
As 6e ha/e seen in Section 27-, in his model o. the hydrogen atom Bohr 0uantised
electronic or3ital angular momentum thirteen years 3e.ore the 3irth o. 0uantum mechanics7
An #$25, .urther studies o. the spectra o. atoms and the e..ect o. magnetic Lelds upon them
led Samuel A3raham Goudsmit (#$02 I #$-%+ and George 'ugene =hlen3ec4 (#$00 I
#$%%+ to postulate that, in addition to its or3ital angular momentum, an electron also
possesses another type o. angular momentum 6hich they called spin angular momentum7
Li4e the or3ital angular momentum, the spin angular momentum also plays a role in the
magnetic properties o. atoms, though the relationship 3et6een the angular momentum and
the magnetism is not eactly the same in 3oth cases (see Section #272+7
Wol.gang !auli (#$00 I #$5%+, 6ho had used the concept o. electron spin to
.ormulate his eclusion principle in #$25, introduced spin into the ne6 0uantum
mechanics t6o years laterP 3ut in a phenomenological manner7 An #$2% <irac placed
the concept on a much Lrmer .ooting 6hen he .ound that the electron2spin 0uantum
num3er arose natu2 rally 6hen the 0uantum mechanics o. the hydrogen atom 6as made
compati3le 6ith the theory o. relati/ity7 <etailed study then re/ealed that the spin angular
momentum o3eyed '0uations (*7*7#+, (*7*72+ and (*7*7,+ eactly as or3ital angular
momentum did, 3ut 6ith one important di..erence7 Dor spin the 0uantum num3er d could
ta4e positi/e hal.2integer as 6ell as integer /alues7 Thus, in addition to the d and m
d
/alues gi/en a3o/e, .or spin 6e can also ha/e1
d
=
#
P m
d
#

+
#
2 2 2
, # # ,
d
=
,
P m
d =

+ +
2 2 2
5 ,
2 2
# # , 5
d
=
5
P m
d =

+ + + etc7
2 2 2 2 2 2 2
(1* T2TA5 ANU5AR M2MENTUM
The total angular momentum o. an atom or molecule is usually composed o. 3oth spin
and or3ital parts and 3oth o. these contri3utions may arise .rom se/eral sources7 Dor
eample, the spin angular momentum may 3e electron spin, 3ut the spins o. the nuclei
are also important in many 3ranches o. atomic and molecular spectroscopy7 "r3ital angular
momentum may 3e due to or3ital motion o. electrons7 At may also arise as a result o.
the rotation in space o. the molecule as a 6hole7 These /arious angular momenta are not
independentP they interact 6ith each other 3y mechanisms o. 6hich 6e shall gi/e some
eamples in the chapters on atomic structure and spectroscopy7 At is important there.ore
that 6e ha/e a 6ay o. adding angular momenta together7
(1*1% T$e a//ition an/ #onserAation o" ang;lar moment;m in
@;ant;m me#$ani#s
An classical mechanics the addition o. t6o angular momenta is 0uite straight.or6ard7 The
tails o. the t6o /ectors are 3rought to the same point and the addition parallelogram
constructed to gi/e their sum7 An Digure *75a, a + b = c 7 Thus, .or any pair o. /ectors a
and b, each o. Led magnitude (length+ and direction (orientation+, there can 3e one, and
only one, resultant (c+7 Angular momentum is conser/ed and c must 3e the /ector sum
o. a and b7 Digure *753 sho6s an alternati/e .orm o. the addition diagram7
The addition o. angular momentum in 0uantum mechanics is not as simple 3ecause all
contri3utions to the total angular momentum are themsel/es 0uantised and the addition
process, also 4no6n as co1%ling, must ensure that the sum itsel. and also its components
are 0uantised7 At can 3e sho6n (Bo *72+
2
that i. t6o angular momenta characterised 3y
the angular momentum 0uantum num3ers d
#
and d
2
are added to .orm a total angular
momentum characterised 3y the 0uantum num3er d , then d can ta4e all the /alues gi/en
3y the '0uation (*7?7#+P also 4no6n as the Cle3sch I Gordan series1
d = d
#
+ d
2
d
#
+ d
2
# d
#
+ d
2
2 . . . |d
#
d
2
| (*7?7#+
e7g7 d
#
=
, d
2
=
# 1 d
=
* , 27 d
#
=
2 d
2
=
,
1 d
=
-

5

,

#
7
2 2 2 2 2
(;ote ho6 the series terminates at the modulus o. the di..erence 3et6een d
#
and d
2
7+
Although d
#
and d
2
are deLned as completely as is possi3le in 0uantum mechanics,
according to '0uation (*7?7#+ 2d
P
+ #, 6here d
P
is the smaller o. d
#
and d
2
, resultants
o. the addition o. d
#
and d
2
are permissi3le, rather than the single resultant 6hich 6e
6ould ha/e in classical mechanics, (Digure *75+7 At is tempting to attempt to dra6 t6o
/ectors ha/ing lengths characterised 3y their /alues o. d
#
and d
2
and orientations 6ith
respect to the B ais determined 3y their /alues o. m
d #
and m
d 2
and to add these in the
classical manner, compara3le to Digure *75, to o3tain a /ector characterised 3y d and m
d
gi/en 3y the rules .or the addition o. 0uantum2mechanical angular momentum 0uoted
a3o/e7 This is not possi3le 3ecause the plane containing the B ais and d
#
cannot 3e
assumed to 3e coincident 6ith that containing the B ais and d
2
7 The rules apply to the
0uantum num3ers and the angular momentum /ectors constructed using them cannot 3e
added as in classical mechanics7 But the B components o. d
#
and d
2
3oth lie along the
B ais and can 3e directly added and each component o. the com3ined /ector,
|
d m
d

,
is a sum o. the components o. the com3ining /ectors,
|
d
#
m
d #

and
|
d
2
m
d 2

,
6hich
includes all those 6hich satis.y the re0uirement that m
d
=
m
d #
+
m
d 2
7 Dor eample, one
can sho6 using the raising and lo6ering operators (Section *7-7# and Bo *7#+ that in the
a c
a
*
*
c
(a+ (3+
6ig;re (1) The addition o. angular momenta in classical mechanics
2
d
#
case o. the second o. the a3o/e eamples the resultant /ector
|
5

+
#

6ith d
=
5
and
m
d
= +
#
, is1
2 2 2
|
2

+
2
=
,

!,,-0"
|
2

#
|
2

+
2
+

!?,-0"
|
2 0
|
2

+
2

5 # , , , #

5,

!-0"
|
2
+
#
|
,


#

2

!,,-0"
|
2
+
2
|
,


,
2 2 2 2
The numerical coe.Lcients in the a3o/e sum are 4no6n as Cle3sch I Gordan
coe.Lcients and .ormulae .or calculating them .rom d , m
d
d
#
m
d #
d
2
and m
d 2
can 3e
.ound in many sources7
2I5
They are also etensi/ely ta3ulated7
?
An spite o. the o3/ious di.Lculty o. illustrating the 0uantum2mechanical addition o.
/ectors, one .re0uently encounters diagrams o. that type and they are /ery help.ul in
understanding comple coupling processes such as are .ound in molecular electronic
spectroscopy7 The 3asic situation is illustrated in Digure *7?7 An Digure *7?(a+ the t6o
/ectors, d
#
and d
2
, are not coupled7 'ach precesses a3out the B ais, independently 6ith
constant B components (&
#
and &
2
+ 3ut not in phase7 d
#
, d
2
, m
#
and m
2
are good
71an+ t1m n1m*ers and the corresponding angular momenta and B components are
separately o3ser/a3le7 An Digure *7?(3+ d
#
and d
2
, are coupled to .orm d, a3out 6hich
they precess together and in phase7 They no longer ha/e constant B componentsP d
#
, d
2
,
m
#
and m
2
are not good 0uantum num3ers and the corresponding angular momenta and
components are not o3ser/a3le7 d precesses a3out B 6ith a constant B component, &, the
0uantum num3ers d and m are good 0uantum num3ers and the corresponding angular
momentum and its B component are eperimental o3ser/a3les7 This point is illustrated
6ith an eample in Section *7?727
"ne other conse0uence o. the .act that, in 0uantum mechanics, there can 3e more
than one result .or the sum o. t6o /ector 0uantities should 3e mentioned here7 We
shall in/estigate it .urther in Chapter % 6hen 6e consider the 0uestion o. the con2
ser/ation o. angular momentum in connection 6ith spectroscopic selection rules7 At
this point 6e need only say that i., 3e.ore a particular e/ent, a system consists o.
t6o angular momenta characterised 3y the angular momentum 0uantum num3ers d
#
and d
2
and i., a.ter the e/ent, the system has an angular momentum characterised
3y d then i. d satisLes any o. the 2d
P
+
# '0uations (*7?7#+, angular momentum has
3een conser/ed7
N N
d
d
# m
# m
m
2
d
2
d
2
(a+ (3+
6ig;re (1* The addition (coupling+ o. t6o angular momenta
(1*1& T$e laws o" @;ant;m9me#$ani#al ang;lar moment;m
"nce 6e ha/e a .ormula .or the addition o. t6o angular momenta 6e can add any num3er
o. contri3utions 3y repeated applications o. the .ormula7 (But note ho6 rapidly the num3er
o. possi3le /alues .or the total angular momentum risesU+
And although there may 3e many contri3utions to the total angular momentum o. a
molecule, 6e can ma4e three general statements a3out angular momentum 6hich each
indi/idual contri3ution to the total and the total itsel. must o3ey7 They are1
#7 The s0uare o. the angular momentum, a
2
, is gi/en in terms o. the 0uantum num3er d
in the .orm o. '0uation (*7*7#+1
a
2
= Zd!d + #"\h`
2
6here d can ta4e any positi/e integer or hal.2integer /alue, including Kero7
27 The components o. the angular momentum, a
B
, in any speciLed direction (con/ention2
ally the B2ais+ are gi/en 3y '0uation (*7*72+1
a
B
= m
d
h`
6here the 0uantum num3er m
d
can ta4e all 2d + # /alues .rom d to +d in unit
steps, '0uation (*7*7,+7
,7 A. the angular momentum is purely or*ital angular momentum the 0uantum num3er d ,
and hence m
d
, can ta4e only integer /alues7 When spin is in/ol/ed hal.2integer /alues
are also possi3le7
These three statements might 3e termed the la6s o. 0uantum2mechanical angular
momentum and t6o important points a3out them should 3e made7 Dirstly, it is rare
to o3ser/e the angular momentum directly, usually it is the transitions 3et6een states
o. angular momentum 6hich gi/e rise to o3ser/a3le eperimental data7 Secondly, in
cases 6here t6o or more angular momenta are com3ined, or co1%led (Section *7?7#+,
the o3ser/a3le eperimental data are related to changes in the total angular momentum
and must 3e interpreted in terms o. the corresponding total 0uantum num3ers7 But the
indi/idual 0uantum num3ers .or the contri3uting angular momenta play an important role
in descri3ing the system theoretically and it is in that sense that 6e can say that the
indi/idual contri3utions to the total angular momentum o3ey the a3o/e la6s, e/en 6hen
they are not eperimentally o3ser/a3le7
At might 3e help.ul to ma4e this point clear 6ith an eample7 An a hea/y atom,
the or3ital angular momentum o. an electron (0uantum num3er l+ may couple 6ith
the spin angular momentum o. the same electron (0uantum num3er s+ to gi/e a total
angular momentum characterised 3y the 0uantum num3er & 7 (See Section 57% .or more
details on this phenomenon 6hich is called s%in+or*it co1%ling7+ 'perimental o3ser2
/ations are interpreta3le in terms o. & 6hich is said to 3e a good 0uantum num3er7
The or3ital and spin angular momenta corresponding to the 0uantum num3ers l and s
only .eature in the theoretical description o. the atom, they are not o3ser/ed directly
in the eperimental measurements and, conse0uently, l and s are not good 0uantum
num3ers7
(1+ ANU5AR M2MENTUM 2!ERAT2RS AN3 EIEN6UNCTI2NS
An Chapter , 6e discussed the 3asic application o. SchroM dingerGs theory o.
o3ser/a3les, operators, eigen.unctions and eigen/alues using eplicit mathematical
.unctions .or the operators .or energy and angular momentum in our eamples7 We
consider these ideas again here 3ecause, .or angular momentum, the concept ta4es an
etremely simple .orm in 6hich, .or many applications, 6e do not need to gi/e .ull
mathematical epressions .or either the operators or the eigen.unctions7 This is /ery
.ortunate, not only on account o. the resulting simplicity 3ut also 3ecause the operators
.or spin angular momentum cannot 3e o3tained .rom the corresponding classical
epressions 3ecause there is no classical analogue o. 0uantum2mechanical spin7
An Bo *7# eigen.unction2eigen/alue e0uations .or the Lrst t6o la6s o. Section *7?
('0uations (B*7#722a+ and (B*7#7223++ are deri/ed7 We repeat those e0uations here 6ith
d

as the operator .or total angular momentum and d

B
that .or its K
component1

and
d

|
d m
d
=
d!d
+
#"

h
`
|
d m
d

!*.-.#"
d

B
|
d m
d
=
m
d

h`
|
d m
d

!*.-.2"
9ere 6e are adopting a notation, Lrst suggested 3y <irac, in 6hich 6e speci.y the eigen2
.unction |d m
d
, solely 3y gi/ing the 0uantum num3ers 6hich deLne it and determine
its eigen/alues7 Angular momentum eigen.unctions are characterised 3y t6o 0uantum
num3ers7 The Lrst (d + gi/es the total angular momentum, in units o. hH2( , according
to '0uation (*7-7#+7 The second (m
d
+ gi/es the B component o. that angular momen2
tum, also in units o. hH2( , according to '0uation (*7-72+7 The corresponding eigen.unc2
tion is eactly identiLed, as .ar as its angular momentum properties are concerned,
i. the /alues o. these t6o 0uantum num3ers are gi/en, and that is .re0uently su.2
Lcient .or our purposes7 The sym3ol
|
d m
d

is there.ore all that 6e need to 6rite
'0uations (*7-7#+ and (*7-72+, 6hich satis.y the re0uirement that the operator operating
on the eigen.unction is e0ual to the eigen.unction multiplied 3y a num3er, the eigen/alue7
The eigen/alues o. the angular momentum operators are the o3ser/a3le, 0uantised /al2
ues o. the total angular momentum and its B component gi/en in units o. h,2( 3y the
0uantum num3ers7
(1+1% T$e raising an/ lowering< s$i"t or la//er operators
Since 6e cannot 4no6 the /alues o. the and y components o. the angular momentum i.
6e already 4no6 the B component, 6e cannot 6rite eigen.unction2eigen/alue e0uations
li4e '0uation (*7-72+ .or d

x
and d

y
7 9o6e/er, there are t6o operators deri/ed .rom d

x
and
d

y
6hich 6e use in Bo *7#7 Although they are not eigen.unction2eigen/alue
e0uations,
they are o. great /alue to us7 The operators are the raising and lo6ering operators, d

+
and d


deLned 3y the e0uations1
and
d

+
= d

x
+ id

y
!*.-.,"
d


= d

x
id

y
!*.-.*"
;otation %,
An these t6o e0uations, i =

! #"P .or more in.ormation a3out i see Appendi %7 The


t6o operators ha/e /ery important properties 6hich are deduced in Bo *7# ('0uations
(*7#7,#a+ and (*7#7,#3++ and repeated here as '0uations (*7-75+ and (*7-7?+1

d

+
|
d m
d
=
Zd!d
+
#"

m
d
!m
d
+
#"\

h
`
|
d m
d
+
#

(*7-75+
d

|d m
d
= Zd!d + #" m
d
!m
d
#"\ h`
|d m
d
# (*7-7?+
The application o. either operator does not change the /alue o. the total angular
momentum (the 0uantum num3er d remains the same+ 3ut each changes the /alue o.
the B component o. the angular momentum 3y one unit o. h,2( 7 d

+
raises the /alue o.
d
B
, i7e7 (m
d

m
d
+
#+, and d


lo6ers it (m
d

m
d

#+7 Dor eample1

d

+
|
2 #
=
Z!2

,"

!#

2"\

h`
|
2 2
=
2h`
|
2 2

|
2 #
=
Z!2

,"

!#

0"\

h`
|
2 0
=
?h`
|
2 0

These are not eigen.unction2eigen/alue e0uations 3ecause the .unctions on the le.t2
and right2hand sides o. '0uations (*7-75+ and (*7-7?+ are not the same7 :ather, these t6o
operators ta4e us up (d

+
+ and do6n (d

+ a set o. m
d
/alues, one step at a time7 They are
there.ore 4no6n as the raising and lo0ering ladder or shift operators7 ;ote that i. 6e
try to raise an m
d
/alue 6hich is already at its maimum, i7e7 m
d
= d , 6e get a result o.
Kero7 The same is true i. 6e try to lo6er a /alue o. m
d
6hich is already at its minimum
/alue, i7e7 m
d
= d 7
(1, N2TATI2N
The 0uantum num3ers d and m
d
in the a3o/e la6s represent any .orm o. angular momen2
tum7 At has 3ecome customary to denote the /arious types o. angular momentum 6ith
a particular choice o. sym3ols .or d as the 0uantum num3er and this practice is so
6idespread and consistent that it should 3e stated here7
The or3ital angular momentum o. an electron in an atom1 l and m
l
7
The spin angular momentum o. an electron1 s and m
s
7
The com3ined spin and or3ital angular momentum o. an
electron in an atom1
Where the angular momentum results .rom more than
one electron this is indicated 3y using the upper case
letters1
& and m
&
7
L, 5
L
, S, 5
S
, Q , 5
Q
7
The spin angular momentum o. an atomic nucleus1 : and 5
:
7
The or3ital angular momentum o. a rotating diatomic
molecule1
The or3ital angular momentum o. a molecule rotating in
space1
Q and 5
Q
7
R and 5
R
7
(An the last three cases the upper case letter is al6ays used, e/en .or one nucleus or
one molecule7+
%* Angular Comentum
=
2
2
,
2
2 2
# ,
" "
2
=
2
2
=
2
#
2
2
= = +
2 2 2
2
(1- S2ME EDAM!5ES
A single electron has s
=
#
and there.ore m
s
#
and +
#
7 Thus, a single electron can
2 2 2
3e .ound in t6o di..erent spin states7 When t6o electrons occupy the same or3ital (spatial
# #
region+ in an atom or molecule one has m
s
=
2
and the other m
s
= +
2
7 They are said
to 3e spin2paired or, simply, paired7
The s, %, d , . . . atomic or3itals o. atoms (see Chapter 5+ ha/e or3ital angular momen2
tum 0uantum num3ers, l = 0 # 2 . . . respecti/ely7 Associated 6ith these there are m
l
/alues o. 0 .or s, #, 0, +# .or % and 2, #, 0, +#, +2 .or d , etc7 Thus, there is @ust
one s or3ital, 3ut there are three % or3itals, L/e d or3itals, se/en f or3itals, . . . 7 The
element 3oron consists o. t6o isotopes, #$7? Y o.
#0
B and %07* Y o.
##
B7 The nuclear
spin 0uantum num3ers o. the t6o isotopes are , and
,
respecti/ely and 6e there.ore
ha/e1
#0
/: = , 5
:
= , 2 # 0 +# +2 +,
##
/: =
,
5
:
=
2


2

+
#
+
,
The rigidity and simplicity o. the rules o. 0uantum2mechanical angular momentum
ma4e more comple systems 0uite easy to handle, in principle, though .re0uently tedious
in practice7 Suppose that 6e ha/e one electron in a % or3ital7 Then, s =
#
and the possi3le
m
s
/alues are
#
and +
#
, 6hile l = # and the possi3le m
l
/alues are #, 0 and +#7
:ecall that the m
s
and m
l
/alues gi/e the components o. the angular momenta along the
B ais7 There.ore, adding the B components o. the or3ital and spin /ectors 6e ha/e si
possi3ilities .or the B component o. the com3ined momenta, m
&
1
m
l
m
s
m
&
# + ! " =
m m
s
m
&
0
+
!

# #
m
l
m
s
m
&
+
#
+
!

# #
2 2 2 2 2 2
# # # # ,

#
+
!
+
#
"
=
0 + !+ " = +
+# + !+
" = +
2 2 2 2 2 2
The result o. adding the B components o. or3ital and spin angular momenta are si
m
&
/alues 6hich represent the B components o. the com3ined angular momenta7 And 6e
4no6 .rom the a3o/e la6s, 6hich angular momentum al0ays o3eys, that the /alues o.
these components must go .rom m
&
to +m
&
in unit steps7 There.ore, i. there is an m
&
/alue o.

,
it must 3e associated 6ith .urther m
&
/alues o.

#

+
#
and
+
,
7 Durthermore,
2 2 2 2
6e also 4no6 that the maimum m
&
/alue 6ill 3e the same as the & /alue .or the total
angular momentum, so 6e ha/e disco/ered that our single % electron can ha/e a state o.
angular momentum characterised 3y the 0uantum num3ers1
& =
,
and m
&
,
#

+
# +
,
We remo/e these .our /alues .rom our list a3o/e (it does not matter 6hich o. the t6o
# #
+
2
and

2
/alues 6e chooseP this is merely a 3oo424eeping eercise+ and there remain
@ust t6o m
&
/alues,

#
and
+
#
7 Clearly, there is a second angular momentum state .or
2 2
our p electron 6hich is characterised 3y the 0uantum num3ers1
& =
#
and m
&
#
+
#
These results .or the possi3le /alues o. & should 3e compared 6ith those o3tained 3y
adding the spin and or3ital angular momenta according to the rule gi/en in Section *7?7#7
#
2
=
2
=
2
#
2 2
7
2
Some 'amples %5
We can apply a similar method to determine the spin states o. a t6o2electron system7
We Lrst ta3ulate all the possi3le com3inations o. m
s#
and m
s2
and their total 5 1
m
s#
m
s2
5 m
s#
m
s2
5 m
s#
m
s2
5
# # # # # #
+
2
+
2
+
#
+
2

2
0

2

2

#

2 2
0
Clearly, the /alue 5 = +# must 3e associated 6ith t6o other components, 5 = 0
and 5 = #7 Thus, there is a state 6ith a total spin o. S = # 6hich, 3ecause it has three
components |# +# |# 0 and |# # , is called a tri%let7 A singlet, |0 0 , 6ith S = 0
and 5 = 0 remains7
To Lnd the eigen.unctions 6e Lrst use the lo6ering operator (S

+ on the com3ined
spin .unction |# +# 1

|
#
+
#
=
#!# + #" #!# #"|# +# = 2|# 0
We no6 apply the lo6ering operators (s

!#" and s

!2"+ to the spin .unctions o.


the indi/idual electrons1
# # # # # #
{
s

!#"
+
s

!2"
}| +
2
!#"
+
2
!2"
=
s

!#"
| +
2
!#"
+
2
!2"
+
s

!2"
| +
2
!#"
+
2
!2"

# # # #
'0uating the t6o results1
= |
2
!#"
+
2
!2"
+ | +
2
!#"

2
!2"


# # # # #
|# 0 =
2
{|
2
!#"
+
2
!2"
+ | +
2
!#"

2
!2"
}
Durther lo6ering operations on 3oth sides o. the a3o/e e0uation gi/e1
|
#

#
= |
#
!#"

#
!2"
2 2
The singlet state, |0 0 , must ha/e 5 = 0 and 3e orthogonal to the state |# 0 7 These
t6o conditions determine its eigen.unction to 3e1

# # # # #
|0 0 =
2
{|
2
!#"
+
2
!2"
| +
2
!#"

2
!2"
}
As a Lnal eample 6e consider the spin properties o. the hydrogen atom 6hich ha/e
some interesting applications7 The nucleus o. the hydrogen atom, the proton, has a spin
o. : =
#
and 5
:
#
and +
#
7 The single electron has s =
#
and m
s
#
and +
#
There.ore, there are .our possi3le spin states o. the hydrogen atom1
5
:
m
s
5 5
:
m
s
5
# # # #

2
+
!

2
"
=
#

2
+
2
=
0
# # # #
+
2
+
!

2
"
=
0
+
2
+
2
= +
#
As al6ays, 6e note that 6e ha/e /alues o. 5
:
+ m
s
6hich run .rom # to +# in
unit steps and 6e pic4 out these as the three components o. a state characterised 3y
a total angular momentum 0uantum num3er o. #7 A spin state o. Kero total angular
momentum remains7 ;o6, 3ecause the spins o. the nucleus and the electron are each
associated 6ith a magnetic moment (see Chapter 5+, the t6o particles 3eha/e as i. they
6ere minute 3ar magnets and the energy o. the atom depends upon the relati/e orientation
o. the t6o magnets7 The energy o. the state in 6hich the t6o spins are aligned parallel,
%? Angular Comentum
# #
e7g7 5
:
= +
2
m
s
= +
2
is greater than that in 6hich the t6o spins are aligned anti2
# #

,0
parallel, e7g7 5
:
=
2
m
s
= +
2
, and the energy di..erence is 0.$*#2

#0 J7 Some
.urther discussion o. the nature o. this interaction can 3e .ound in Section $7?7 =sing
the Bohr2'instein e0uation, E = h>, (Section 27-7#+ this energy di..erence corresponds
to electromagnetic radiation o. .re0uency #*207* C9K or 6a/elength 072### m7 Thus,
i. the higher energy state should change into the lo6er energy state, i7e7 i. the relati/e
orientations o. the t6o spinning particles 6ere to change .rom parallel to anti2parallel,
then electromagnetic radiation o. the a3o/e .re0uencyH6a/elength 6ould 3e emitted7
An #$*2, 9endri4 8an de 9ulst (#$#% I + suggested that, although this e/ent
6ould
occur only /ery in.re0uently (approimately once e/ery ## million years in any one
hydrogen atom+, since there are /ast amounts o. hydrogen distri3uted as atoms throughout
space, one might epect to detect this radiation i. a su.Lciently sensiti/e recei/er 6as
a/aila3le7 Dollo6ing World War AA, the technological ad/ances achie/ed in pursuit o.
military o3@ecti/es made the rapid de/elopment o. radio astronomy possi3le and the
Qsong o. hydrogenG 6as detected and used to map the galay7
Later, in the #$?0s, 6hen it 6as proposed that 6e might listen .or radio transmissions
.rom intelligent 3eings in outer space the 0uestion naturally arose as to 6hat .re0uency
o. signal the listening de/ice should 3e tuned to recei/e7 At 6as persuasi/ely argued that,
since hydrogen is the most a3undant element in the uni/erse, the emissionHa3sorption o.
hydrogen atoms 6ould 3e 4no6n to all intelligent li.e and that this 6as there.ore the
.re0uency 6hich should 3e used7 The search has no6 occupied more than #0 000 hours
o. radio2telescope time 6ith the star systems E%silon Eridani and -a1 Ceti (## and #2
light years distant respecti/ely+ as the main targets7 All results to date ha/e apparently
3een negati/e7
An #$$* the 072### m emission o. hydrogen atoms 6as used to disco/er a ne6 galay,
<6ingeloo #, 6hich is a3out #0
-
light years .rom earth and lies in the plane o. our o6n
galay, the Cil4y Way7 Star systems 6hich lie 6ithin the Cil4y Way are /ery di.Lcult
.or us to see 3ecause 6e ha/e to loo4 through the plane o. the galay and the scattering
o. light 3y dust particles 6ithin the plane o3scures the image7 But the scattering o. light
is in/ersely proportional to the .ourth po6er o. the 6a/elength (:ayleighGs La6+ so that
the scattering o. the long26a/elength hydrogen emission is scarcely a..ected 3y the dust7
By searching .or the 072### m 6a/es .rom 6ithin the galactic plane, astronomers in the
;etherlands 6ere a3le to detect the emission .rom <6ingeloo # and pin2point its position7
When this had 3een done it 6as possi3le to conLrm the disco/ery 3y means o. a rather
poor image o3tained 6ith an optical telescope7 The search .or 072### m emission .rom
other galaies 6ithin the Cil4y Way continues7
(1%. 8I85I2RA!HY AN3 6URTHER REA3IN
#7 A7J7 CcCa..ery, N7T7 Al6aha3i, C7A7 "s3orne and C7J7 Williams, Q. Chem. Physics, -,, *5%?,
#$$,7
The comparati/ely recent 3oo4 3y Nare
2
co/ers a /ery large area o. angular momentum theory
and highlights many applications in physics and chemistry7 At can 3e highly recommended to
those 6ho 6ish to study angular momentum theory and to apply it to the interpretation o. physical
measurements7 'arlier, classic tets on the su3@ect are those 3y :ose,
,
'dmonds
*
and 3y Brin4
and Satchler7
5
Bouten
-
has pointed out that there are, un.ortunately, some inconsistencies in the
treatment o. rotations 3y 3oth :ose and 'dmonds, 3ut one has to 3e an ad/anced user o. the
theory to appreciate or 3e a..ected 3y this pro3lem7
27 :7;7 Nare, Ang1lar 5oment1m, Wiley, ;e6 Ror4, #$%%7
,7 C7'7 :ose, Elementary -heory of Ang1lar 5oment1m, Wiley, ;e6 Ror4, #$5-7
*7 A7:7 'dmonds, Ang1lar 5oment1m in 31ant1m 5echanics, !rinceton =ni/ersity !ress, #$5-7
57 <7C7 Brin4 and G7:7 Satchler, Ang1lar 5oment1m, 2nd 'dn, ".ord =ni/ersity !ress, #$?27
?7 :7<7 Co6an, -he -heory of Atomic Str1ct1re and S%ectra, Cali.ornia =ni/ersity !ress, Ber4eley,
#$%#7
-7 C7 Bouten, Physica, (&, 5-2, #$?$7
82D (1% Ang;lar moment;m operators an/ #omm;tation r;les
The or3ital angular momentum (L+ o. a single particle a3out an origin is the /ector
product o. the distance .rom the origin (r+ and the linear momentum (p+1
L = r p (B*7#7#+
An Cartesian co2ordinates the components o. L are1
L
x
= y%
B
B%
y
(B*7#72a+
L
y
= B%
x
x%
B
(B*7#723+
L
B
= x%
y
y%
x
(B*7#72c+
;ote ho6 the successi/e components can 3e o3tained 3y a cyclic permutation o.
x y B x . . .
A. 6e replace the %Gs 3y the corresponding 0uantum2mechanical operators 6e
o3tain the operators .or angular momentum in units o. h,2( h` 1
L

x
= ih`
{yD,D B BD,Dy} (B*7#7,a+
L

y
= ih`
{BD,D x xD,D B} (B*7#7,3+
L

B
= ih`
{xD,Dy yD,D x} (B*7#7,c+
These three operators do not commute 6ith each other, .or eample1
L

x
L

y
= h`
2
{yD,D B BD,Dy}{BD,D x xD,D B}
= h
`
2
{yD,D BZBD,D x\ yD,D BZxD,D B\ BD,DyZBD,D x\ + BD,DyZxD,D B\}
The terms in s0uare 3rac4ets must 3e di..erentiated as products so that 6e ha/e1
= h
`
2
{yD,D x + yBD
2
,D BD x yx D
2
,D B
2
B
2
D
2
,DyD x + BxD
2
,DyD B}
Similarly1
L

y
L

x
= h`
2
{BD,D x xD,D B}{yD,D B BD,Dy}
= h
`
2
{BD,D xZyD,D B\ BD,D xZBD,Dy\ xD,D BZyD,D B\ + xD,D BZBD,Dy\}
= h`
2
{ByD
2
,D xD B B
2
D
2
,D xDy xy D
2
,D B
2
+ xD,Dy xBD
2
,D BDy}
The co2ordinates x, y and B commute 6ith each other and so do the operators
.or partial di..erentiation 6ith respect to those co2ordinates7 There.ore, yBD
2
,D BD x =
ByD
2
,D xD B etc7 and1
{L

x
L

y
L

y
L

x
} = h`
2
{yD,D x xD,Dy} = ih`
ih`
{xD,Dy
yD,D x}
= ih` L

B

Thus1
{L

x
L

y
L

y
L

x
} ZL

x
L

y
\ = ih
`
L

B

!B*.#.*a"
and similarly1
and1
{
L

y
L

B

L

B
L

y
}


ZL

y
L

B
\
=
ih
`
L

x

{L

B
L

x
L

x
L

B
} ZL

B
L

x
\ = ih` L

!B*.#.*3"
!B*.#.*c"
These are the commutation relationships 3et6een the operators .or the Carte2
sian components o. angular momentum7 The sym3ol Za *\ = a* *a, is called the
commutator o. a and *7
But L

2
=
L

2
+
L

2
+
L

2
commutes 6ith each o. its components, e7g7
Zdropping
x y B
the eplicit inclusion o. the operand, , to simpli.y the notation\1
L

2
L

B

L

B
L

2
=
L

2
L
B
+
L
2
L
B
+
L
,

L
B
L
2

L
B
L
2

L
,
x

y

B

x

y

B
= L

x
L

x
L

B
L

x
L

B
L

x
+ L

x
L

B
L

x
L

B
L

x
L

x
+ L

y
L

y
L

B
L

y
L

B
L

y
+ L

y
L

B
L

y
L

B
L

y
L

y
= L

x
!ih` L

y
" + !ih` L

y
"L

x
+ L

y
!ih` L

x
" + !+ih` L

x
"L

y
= 0
An the second line a3o/e 6e ha/e su3tracted and then added L

x
L

B
L

x
and L

y
L

B
L

y
7
An summary1
ZL

2
L

x
\ = ZL

2
L

y
\ = ZL

2
L

B
\ = 0
(B*7#75+ ZL

also commutes 6ith each o. its components 3ut it is simpler to 6or4
6ith L
2
\7
Drom '0uations (B*7#75+ 6e 4no6 (Section ,7##+ that there is a set o. .unctions
6hich are simultaneously eigen.unctions o. 3oth L

B
and L
2
7 A. 6e use the
correspond2
ing 0uantum num3ers, 5 and L, to characterise these .unctions 6riting them in the
.orm |L 5 , 6e ha/e the .ollo6ing t6o eigen/alue2eigen.unction e0uations, 6here
@
L
and @
5
are the eigen/alues .or the s0uare o. the total angular momentum, in
units o. h`
2
, and its B component, in units o. h` , respecti/ely1
L
2
|L 5 = @
L
|L 5 !B*.#.?"
and
L

B
|L 5 = @
5
|L 5 !B*.#.-"
Starting .rom these e0uations 6e can no6 deduce the most important properties
o. the angular momentum eigen/alues1
L

2
|
L 5
= {
L

2
+
L

2
+
L

2
}|
L 5
=
@
L
|
L 5

!B*.#.%"
x y B
and L

B
L

B
|L 5 = L

B
@
5
|L 5 = !@
5
"
2
|L 5 !B*.#.$"
Su3tracting '0uation (B*7#7$+ .rom '0uation (B*7#7%+ 6e o3tain1
{
L

2
+
L

2
}|
L 5
= {
L

2

L

2
}|
L 5
= {
@
L

!@
5
"
2
}|
L 5

(B*7#7#0+
x y B
Thus, the .unctions
|
L 5

are also eigen.unctions o. L

2
+
L

2
and the eigen/alues
x y
o. the sum o. the s0uares o. t6o angular momentum components must 3e positi/e so
that1
@
L
!@
5
"
2
(B*7#7##+
B
+
We no6 deLne t6o ne6 operators, the raising and lo6ering, ladder or step
operators1
and
and
L

+
= L

x
+ iL

y
!B*.#.#2a" L


= L

x
iL

y
!B*.#.#23"
=sing the commutation rules B*7#7* one can readily sho6 that1
L

B
!L

x
+ iL

y
" = !L

x
+ iL

y
"!L

B
+ h` "
!B*.#.#,a" L

B
!L

x
iL

y
" = !L

x
iL

y
"!L

B
h` "
!B*.#.#,3"
A. the Lrst o. these t6o se0uences o. operations is applied to the .unctions |L 5
6e ha/e1
L

B
!L

x
+ iL

y
"|L 5 = !L

x
+ iL

y
"!L

B
+ h
`
"|L 5 = !L

x
+ iL

y
"!@
5
+ h
`
"|L 5
= !@
5
+ h` "!L

x
+ iL

y
"|L 5 = !@
5
+ h` "L

+
|L 5
(B*7#7#*a+
Thus, !L

x
+ iL

y
"|L 5 is .ound to 3e an eigen.unction o. L

B
6ith an
eigen/alue
o. (@
5
+ h
`
+7 Since L
2
commutes 6ith L

x
and L

y
it also commutes
6ith L

and the
eigen.unction !L

x
+
iL

y
"
|
L 5

remains an eigen.unction o. L
2
6ith eigen/alue @
L
7
Similarly, 6e Lnd that !L

x

iL

y
"
|
L 5

is an eigen.unction o. L

B
6ith an eigen/alue
o. (@
5

h` + 6hile remaining an eigen.unction o. L

2
6ith eigen/alue @
L
1
L

B
!L

x
iL

y
"|L 5 = !@
5
+ h
`
"!L

x
iL

y
"|L 5 = !@
5
h
`
"L


|L 5
(B*7#7#*3+
There.ore, 6e ha/e a series o. eigen.unctions o. L
2
and L

B
, all 6ith the
eigen/alue
o. >
L
.or L
2
3ut 6ith the .ollo6ing se0uence o. eigen/alues o. L

B
1
. . . !@
5
,h` " !@
5
2h` " !@
5
h` " @
5
!@
5
+ h` " !@
5
+ 2h` " !@
5
+ ,h` " . . .
The series must terminate at 3oth ends 3ecause @
L
!@
5
"
2
7 Thus, i. 6e denote
the highest /alue 3y @
5

and the lo6est 3y @
5

the .ull se0uence is1
@
5

. . . !@
5
2h` " !@
5
h` " @
5
!@
5
+ h` " !@
5
+ 2h` " . . . @
5

(B*7#7#5+ There.ore, i. the corresponding eigen.unctions are |L 5

and |L 5


6e must
ha/e1
and
L

+
|L 5

= 0 !B*.#.#?a"
L

|L 5

= 0 !B*.#.#?3"
Applying L


to '0uation (B*7#7#?a+ 6e ha/e1
L

L

+
|L 5

= !L

x
iL

y
"!L

x
+ iL

y
"|L 5


= {
L
2
+
L
2
+
i!L
x
L
y

L
y
L
x
"
}|
L 5

= {
L
2
+
L
2

h
`
L
B
}|
L 5


x y x y
= {L
2
L
2
h
`
L

B
}|L 5

= {@
L
!@
5

"
2
h
`
@
5

}|L 5

= 0
Thus, @
L
= !@
5

"
2
+ h` @
5

!B*.#.#-a"
By operating 6ith L

+
on '0uation (B*7#7#?3+ 6e can also sho6 that1
@
L
= !@
5

"
2
h
`
@
5

(B*7#7#-3+
An order to satis.y '0uations (B*7#7#-a+ and (B*7#7#-3+ and to 3e consistent
6ith the assumption that @
5

P @
5

6e must ha/e @
5

= @
5

7 Durthermore,
the se0uence ('0uation (B*7#7#5++ re0uires that @
5

3e greater than @
5

3y an inte2
gral num3er o. units o. h
`
7 Thus, @
5

must 3e o. the .orm
nh
`
6here n is an integer,
including 0, or a hal.2integer7 Thus .ar 6e ha/e attached no particular signiLcance to
L7 There.ore, since @
5

depends only on L 6e may set n
=
L and 6e ha/e1
@
5

= Lh
`
=sing '0uation (B*7#7#-a+ @
L
= !Lh
`
"
2
+ h
`
Lh
`
!B*.#.#%"
or @
L
= L!L + #"h
`
2
!B*.#.#$"
;o6, the possi3le /alues o. >
5
are1
Lh
`
!L #"h
`
. . . !L
#"h
`
Lh
`
(B*7#720+
And 5 , to 6hich 6e ha/e attached no particular signiLcance yet, can 3e used to
characterise this se0uence o. >
5
/alues1
@
5
= 5 h` L 5 L
(B*7#72#+
A. L is an integer 5 is an integer, i. L is hal.2integral so too is 5 7
'0uations (B*7#7?+ and (B*7#7-+ may no6 3e 6ritten1
L
2
|L 5 = L!L+#"h`
2
|L 5 !B*.#.22a"
and
L

B
|L 5 = 5 h
`
|L 5 !B*.#.223"
These results ha/e 3een deri/ed solely .rom the commutation relationships and
they there.ore apply to any properties .or 6hich the corresponding operators ha/e the
same commutation rules7 At is .ortunate that they also apply to the property 6hich 6e
call QspinG7 Since spin is a non2classical 0uantity, there 6as no reason to assume that
the rules deduced here, 3ased on the classical mechanics o. or3ital angular momentum,
6ould apply7 9o6e/er, it can 3e sho6n using a method 6hich does not depend on
classical mechanics that the commutation rules deduced a3o/e also apply to spin7
Treatments o. this type are 3ased on the theory o. inLnitesimal rotations and can
3e .ound in any o. the re.erences 2 I 5 cited in the 3i3liography o. Chapter *7
The mathematics used is not as daunting as the 6ords QinLnitesimal rotationsG may
ma4e it appear7
The primary tas4 o. this Bo, the deduction o. the commutation rules .or or3ital
angular momentum and .rom them '0uations (B*7#722a+ and (B*7#7223+, has no6
3een accomplished7 But in the process 6e ha/e also Qdisco/eredG the raising and
lo6ering operators, L

+
and L

, 6hich 6e Lnd etremely use.ul throughout this


3oo47
We are no6 in a position to eamine their properties a little more closely7 We .ound
that, in units o. h` , 6hen L

+
is applied to |L 5 6e o3tain an eigen.unction o. L

B
6ith an eigen/alue o. (5 + #+ 6hich is still an eigen.unction o. L
2
6ith the same /alue
o. the 0uantum num3er L7 Similarly, 6e .ound that L

|
L 5

is an eigen.unction
o.
2
2
2
2
L
2
, 6ith the same /alue o. L, and o. L

B
6ith an eigen/alue o. (5 #+7 '0uations
(B*7#72,a+ and (B*7#72,3+ summarise these statements1
L

+
|L 5 = C
+
|L 5 + # (B*7#72,a+
L

|L 5 = C

|L 5 # (B*7#72,3+
C
+
and C

are num3ers 6hich may result .rom the operation 3y L

+
and L


on
|L 5 7 The statements immediately a3o/e 6ould not 3e in/alidated i. the resulting
eigen.unctions 6ere multiplied 3y such constants and 6e need to determine their
/alues7 The comple con@ugate (Appendi %+ o. '0uation (B*7#72,a+ is1
{L

+
|L 5 }

= {C
+
|L 5 + # }

(B*7#72*+ But
{L

+
}

= L

, |L 5

= L 5 | and |L 5 + #

= L 5 + #|, and '0uation
(B*7#72*+ can 3e 6ritten1
L 5 |L


= C
+

L 5 + #| (B*7#725+ A.
6e no6 multiply the right2 and le.t2hand sides o. '0uation (B*7#72,a+, on the
le.t, 3y the same sides o. '0uation (B*7#725+ 6e o3tain '0uation (B*7#72?+1
L 5 |L

L

+
|L 5 = C
+
C
+

L 5 + #|L 5 + # = C
+
C
+

(B*7#72?+
The right2hand side reduces to C
+
C
+

3ecause L|K means integrate the product
LK o/er all space and there.ore L 5 + #|L 5 + # = # i. the eigen.unctions are
normalised, 6hich 6e certainly re0uire them to 3e7 The operator product L

L

+
can
3e e/aluated using '0uations (B*7#7*+ and (B*7#7#2+ and 6e Lnd, in units o. h
`
, that1
There.ore1
L

L

+
=
L

L

B
L

B
(B*7#72-+
L 5 |L

L

+
|L 5 = L 5 |
L

L

B
L

B
|L 5
= L 5 |L!L + #" 5
2
5 |L 5 = L!L + #" 5!5 + #"
(B*7#72%+
since L 5 |L 5 = # .or normalised eigen.unctions7 Dinally, comparing '0ua2
tions (B*7#72?+ and (B*7#72%+ 6e ha/e1
C
+
C
+

= L!L + #" 5!5 + #"
There.ore, since there is no reason to assume that C
+
is anything other than real1
#
C
+

=
C
+
= {
L!L
+
#"

5!5
+
#"
} 2
(B*7#72$+
An analogous de/elopment starting .rom '0uation (B*7#72,3+ gi/es1
#
C


=
C

= {
L!L
+
#"

5!5

#"
} 2
(B*7#7,0+
and the complete .orms o. '0uations (B*7#72,a+ and (B*7#72,3+ are1
#
L

+
|
L 5
= {
L!L
+
#"

5!5
+
#"
} 2 |
L 5
+
#

(B*7#7,#a+
#
L

|
L 5
= {
L!L
+
#"

5!5

#"
} 2 |
L 5

#

(B*7#7,#3+
:eaders may ha/e 6ondered 6hy the positi/e sign 6as chosen .or the s0uare root
in '0uation (B*7#72$+7 There is deLnitely an element o. choice here and, since the
raising and lo6ering operators lin4 all the 2L + # eigen.unctions o. the mani.old o. 5
/alues ha/ing the same /alue o. L, it is important7 This choice o. phase does not a..ect
the calculation o. any measura3le physical property, 3ut it does a..ect intermediate
alge3raic results 6hich can 3e /ery important 6hen these results ha/e 3een ta3ulated
.or general use, as many ha/e 3een7 The positi/e sign 6as Lrst chosen 3y Condon
and Shortley
#
and is no6 e..ecti/ely uni/ersal7
An the light o. the a3o/e a reader might 6ell as4, QA. 6e can Lnd out so much a3out
angular momentum simply 3y studying the commutation properties o. the associated
operators can 6e not approach other 0uantum2mechanical pro3lems in the same 6ayJG
The short ans6er to that 0uestion is QyesG, the procedure is sometimes called second
71antisation7 The 3est24no6n eample o. it is the deduction o. the energy le/els o.
the harmonic oscillator7
2
An that pro3lem the raising operator is 4no6n as the creation
operator 3ecause each application generates an additional /i3rational 0uantum7 The
lo6ering operator, each application o. 6hich remo/es a /i3rational 0uantum, is called
the annihilation operator7 These concepts ha/e /ery 6ide applica3ility and .orm the
3asis o. the description o. photons in the theory o. 0uantum electrodynamicsP see
Section %7$ and re.erence 27 Some less 6ell24no6n applications ha/e 3een descri3ed
3y ;e6march and Golding7
,
#7 '7=7 Condon and G797 Shortley, -he -heory of Atomic S%ectra, Cam3ridge =ni/ersity !ress,
#$,57
27 ;7 Nettili, 31ant1m 5echanics Conce%ts and A%%lications, Wiley, Chichester, 200#7
,7 J7<7 ;e6march and :7C7 Golding, American Q. Phys., (*, ?5% I ??0 #$-%7
82D (1& T$e Cle?s#$ I or/an series
The mathematical proo. o. the Cle3sch I Gordan .ormula .or the addition o.
angu2 lar momenta in 0uantum mechanics is really only a rigorous argument
along the .ollo6ing, more descripti/e, lines7
Suppose that the t6o angular momenta to 3e added are characterised 3y total
angular momentum 0uantum num3ers d
#
and d
2
7 We 6ish to sho6 that the 0uantum
num3ers o. the resulting /ectors, d , are gi/en 3y the Cle3sch I Gordan series1
d = d
#
+ d
2
d
#
+ d
2
# d
#
+ d
2
2 . . . |d
#
d
2
|
The B2components o. the resulting /ectors, characterised 3y their m
d
/alues, must
simply 3e sums o. the B2components o. d
#
and d
2
and there are !2d
#
+ #" !2d
2
+ #"
such sums7 We Lrst arrange the possi3le sums in a rectangular array7
d
#
d
#
# d
#
2 d
#
, d
#
+ # d
#
d
2
d
#
+ d
2
d
#
+ d
2
# d
#
+ d
2
2 d
#
+ d
2
, d
2
d
#
+ # d
2
d
#
d
2
# d
#
+ d
2
# d
#
+ d
2
2 d
#
+ d
2
, d
#
+ d
2
* d
2
d
#
d
2
d
#
#
d
2

2 d
#
+
d
2

2 d
#
+
d
2

, d
#
+
d
2

* d
#
+
d
2

5

d
2

d
#

# d
2

d
#

2
. . . . . . .
d
2
+ # d
#
d
2
+ # d
#
d
2
d
#
d
2
# d
#
d
2
2 d
2
d
#
+ 2 d
2
d
#
+ #

d
2
d
#

d
2
d
#

d
2

# d
#

d
2

2 d
#

d
2

,

d
2

d
#
+
#

d
2

d
#
!ro3lems .or Chapter * $,
2
2 2
2
We no6 go through a procedure 6hich is repeated se/eral times in the eamples
in Section *7$7 At the top le.t corner o. the array 6e Lnd the maimum possi3le
m
d
/alue o. d
#
+
d
2
6hich means that there must 3e a /alue o. d e0ual to d
#
+
d
2
6ith 2!d
#
+
d
2
"
+
# B2components running in unit steps .rom d
#
+
d
2
to

!d
#
+
d
2
"7
We can Lnd this se0uence o. m
d
/alues along the top ro6 and do6n the .ar right
column o. our array and 6e tic4 them o..7 The maimum m
d
/alue remaining in
the array is no6 d
#
+ d
2
#, again in the top le.t corner, and 6e can tic4 o.. the
other 2!d
#
+ d
2
#"m
d
/alues 6hich 6e Lnd in the second ro6 o. the array and the
column second .rom the right7
This process can 3e repeated until 6e ha/e one o. t6o possi3le scenarios7 A. d
#
=
d
2
the last element remaining in the array is the 3ottom le.t corner, d
#
d
2
, 6hich
clearly corresponds to a /ector 6ith d = 0 and m
d
= 07 A. d
#
R d
2
and d
#
d
2
= n
the num3er o. colums eceeds the num3er o. ro6s 3y 2d
#
+ # !2d
2
+ #" = 2!d
#

d
2
" = 2n7 Then the Lnal situation is that 2n + # elements remain at the le.t2hand
end o. the last ro6 o. the array, d
#
d
2
3eing the Lrst o. these and d
#
d
2
2n =

!d
#

d
2
" the last7 These are the m
d
/alues o. a /ector 6ith d
=
d
#

d
2
7
!R285EMS 62R CHA!TER (
#7 :ead Bo *72 and, .ollo6ing the general description o. the addition o. t6o angular
momenta, 6or4 through the speciLc eample d
#
= 2 and d
2
=
,
7
27 =se '0uation (*7#72+ to deri/e an e0uation .or the angular momentum o. a rotating
diatomic
#?
" molecule in terms o. the mass o. the
#?
" atom (2?.5?0#$ #0

2-
4g+,
the 3ond length (#.20-52 #0

#0
m+ and the .re0uency, >, o. the rotation7 The angular #
momentum (L+ must 3e 0uantised according to the e0uation L
=
!h,2( "!Q ZQ
+
#\"
2
7
Dind the rotational .re0uency .or Q = #7
,7 =se '0uations (*7-75+ and (*7-7?+ to determine the e..ects o. the raising and lo6ering
operators on the se/en .2or3ital .unctions, |, m
d
, m
d
= , to +,7
*7 The three e0ui/alent protons o. a methyl group couple to gi/e eight (2 2 2+ nuclear
spin .unctions7 =se an etension o. the method descri3ed in Section *7$ to sho6 that
the coupled spins .orm a state ha/ing S =
,
and t6o states ha/ing S =
#
7 Why do
you thin4 that these states are sometimes descri3ed as Qa 0uartet and t6o dou3letsG J
:epeat the eercise using successi/e applications o. '0uation (*7?7#+7
57 An pro3lem * the spin states, |S 5
S
, o. three e0ui/alent coupled protons ha/e 3een
determined7 A more detailed description o. the system re0uires the eact com3inations
o. the eight nuclear spin .unctions 6hich .orm a particular spin state7 The raising and
lo6ering operators may also 3e used to sol/e this pro3lem7
a+ Starting 6ith the eigen.unction
|
,

+
,

, apply the lo6ering operator, S

, succes2
2 2

si/ely to o3tain the other three eigen.unctions 6ith S


=
,
, e7g71
, ,

, #
S

|
2

+
2
=
,
|
2

+
2

!#"
2
The multiplying .actors 6hich arise 6hen each eigen.unction is generated .rom the
one a3o/e are important7
The only 6ay in 6hich the eigen.unction
|
,

+
,

can 3e generated .rom three
2 2
nuclear spins 6ith s
=
#
is .or all three B2components to 3e parallel, i7e71
, , # # #
|
2

+
2
= | +
2
!#"
+
2
!2"
+
2
!,"

6here only the m
s
/alues o. the indi/idual protons ha/e 3een indicated7 To operate
on the eigen.unction .ormulated as it is on the right o. the a3o/e e0uation 6e 6rite
S


in terms o. the indi/idual spin operators, s

(a+, a
=
#, 2, ,, as1
S


= s

!#" + s

!2" + s

!,"
'ach indi/idual spin operator operates only on a particular spin so that 6e ha/e1
# # #
# # #
{
s

!#"
+
s

!2"
+
s

!,"
}| +
2
!#"
+
2
!2"
+
2
!,"
=
s

!#"
| +
2
!#"
+
2
!2"
+
2
!,"

# # #
# # #
+
s

!2"
| +
2
!#"
+
2
!2"
+
2
!,"
+
s

!,"
| +
2
!#"
+
2
!2"
+
2
!,"

# # #
# # #
= |
2
!#"
+
2
!2"
+
2
!,"
+ | +
2
!#"

2
!2"
+
2
!,"

# # #
+ | +
2
!#"
+
2
!2"

2
!,"

(2+
Comparing the right2hand sides o. e0uations # and 2 6e see that1
, #

# # #
|
2

+
2
= {
#, ,
}{|
2
!#"
+
2
!2"
+
2
!,"

# # #
# # #
+ | +
2
!#"

2
!2"
+
2
!,"
+ | +
2
!#"
+
2
!2"

2
!,"
}
3+ Continue the process to determine the eigen.unctions
|
,


#

and
|
,


,

in
terms
2 2 2 2
o. the indi/idual spin .unctions7 Alternati/ely, start 6ith
|
,


,

and use S

7
2 2
+
c+ To Lnd the t6o dou3lets 6e re0uire t6o epressions .or
|
#

+
#

6hich are nor2
2 2
malised and orthogonal to each other and to
|
,

+
#

7 Try1
2 2

{#,
?
}{
2
|
#
!#"
+
#
!2"
+
#
!,"
| +
#
!#"

#
!2"
+
#
!,"

2 2 2
# # #
2 2 2
and
| +
2
!#"
+
2
!2"

2
!,"
}

{#,
2
}{| +
#
!#"

#
!2"
+
#
!,"
| +
#
!#"
+
#
!2"

#
!,"
}
2 2 2 2 2 2
Sho6 that these t6o .unctions ha/e the re0uired properties o. normalisation and
orthogonality and Lnd the corresponding t6o .unctions |
#

#
3y applying
the
2 2
lo6ering operators to the t6o
|
#

+
#

.unctions7
2 2
Chapter 5
T$e Str;#t;re an/ Spe#tros#op0
o" t$e Atom
570 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $?
57# The eigen/alues o. the hydrogen atom . . . . . . . . . . . . . . . . . . . . . . . . . $?
572 The 6a/e .unctions o. the hydrogen atom . . . . . . . . . . . . . . . . . . . . . . $-
5727# The radial .unction, R
nl
!r " . . . . . . . . . . . . . . . . . . . . . . . . . . $%
57272 The angular .unctions,
lm
!# " and
m
!$" . . . . . . . . . . . . . . . . $$
57, !olar diagrams o. the angular .unctions . . . . . . . . . . . . . . . . . . . . . . . . #00
57,7# The s2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0#
57,72 The %2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0#
57,7, The d 2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0,
57* The complete or3ital 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . #0*
575 "ther one2electron atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0*
57? 'lectron spin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #05
57- Atoms and ions 6ith more than one electron . . . . . . . . . . . . . . . . . . . . #05
57-7# The sel.2consistent Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0?
57-72 'lectron correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0?
57-7, The periodic ta3le o. the elements . . . . . . . . . . . . . . . . . . . . . . #0-
57% The electronic states o. the atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0-
57%7# The L/e 0uantum num3ers o. a single electron . . . . . . . . . . . . . #0%
57%72 &uantum num3ers .or the many2electron atom . . . . . . . . . . . . . . #0%
57%7, The assignment o. term sym3ols . . . . . . . . . . . . . . . . . . . . . . . #0%
57%7* Term energies and 9undGs rules . . . . . . . . . . . . . . . . . . . . . . . ##0
57$ Spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ###
57$7# :ussell I Saunders or LS coupling . . . . . . . . . . . . . . . . . . . . . . ###
57$72 && coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##2
57$7, Antermediate coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##,
57$7* Anter2electronic spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . ##5
57#0 Selection rules in atomic spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . ##5
57#07# Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##5
57#07#7# 'lectric 0uadrupole transitions . . . . . . . . . . . . . . . . . ##?
57#07#72 Cagnetic dipole transitions . . . . . . . . . . . . . . . . . . . . ##?
57#072 !arity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##?
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
$? The Structure and Spectroscopy o. the Atom
57## The Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##-
57##7# The normal Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . ##%
57##72 The anomalous Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . #20
57#2 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2#
!ro3lems .or Chapter 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2$
)1. INTR23UCTI2N
An #$2?, the structure o. the hydrogen atom, and an interpretation o. the 6a/elengths o.
the /isi3le spectral lines o. the atom, 6as pro3a3ly the most immediate pro3lem .acing the
ne6 0uantum mechanics7 An his paper o. #$2?, in 6hich he inaugurated that .ormulation
o. 0uantum mechanics 6hich 6e no6 call 6a/e mechanics, SchroM dinger proposed
the correct .orm o. the 9amiltonian operator .or the pro3lem, deri/ed the re0uired
eigen/alues and eigen.unctions and sho6ed that the .ormer corresponded to the energy
le/els o. the Bohr model o. the hydrogen atom and 6ere there.ore in agreement 6ith the
eperimental data7 These results play a central role in our understanding o. the structure
o. all atoms7 The solution o. the SchroM dinger e0uation .or the hydrogen atom is a
straight.or6ard 3ut time2consuming tas4 and 6e shall not enter into it here7 Dull
details can 3e .ound in many tets7
#2
We shall 3e much more concerned, in this chapter
and in others, 6ith the .ollo6ing aspects o. the pro3lem and their implications .or our
understanding o. atomic structure, atomic spectroscopy, the periodic ta3le and the nature
o. the chemical 3ond7
What are the eigen/alues and ho6 are they determined 3y the 0uantum num3ersJ
What are the .orms o. the corresponding eigen.unctions and 6hat do they tell us a3out
the distri3ution o. the electron in space around the nucleus o. the atomJ
9o6 are the eigen/alues and eigen.unctions o. the hydrogen atom, a one2electron atom,
modiLed 3y inter2electronic repulsion in atoms 6hich ha/e more than one electronJ
What are the magnetic properties o. electrons and ho6 do they mani.est themsel/es in
the structures and spectra o. atomsJ
)1% THE EIENVA5UES 26 THE HY3R2EN AT2M
A. 6e assume that the nucleus has an inLnite mass (see Section 575 .or .urther details+,
then the eigen/alues o. the hydrogen atom are gi/en 3y a simple .ormula 6hich depends
upon @ust one 0uantum num3er (n+ 6hich is 4no6n as the %rinci%al 0uantum num3er7 At
can ta4e any positi/e integer /alue .rom # to 1
E
n
= m
e
e
*
,%h
2
?
0
2
n
2
in J or m
e
e
*
,%ch
,
?
0
2
n
2
in cm

#
(57#7#+
m
e
is the mass o. the electron, e its charge, c the /elocity o. light (in cm s

#
+, h !lanc4Gs
constant and ?
0
the permitti/ity o. a /acuum7 ;ote that the energy is a negati/e 0uantity7
This deri/es .rom the .act that our energy Kero is deLned to 3e the state in 6hich the proton
and electron are inLnitely .ar apart and motionless so that they ha/e neither potential nor
4inetic energy7 As the t6o particles approach each other, the energy o. the .orming atom
The Wa/e Dunctions o. the 9ydrogen Atom $-
decreases 3ecause o. the negati/e coulom3ic energy o. the opposite chargesP so much is
0uite o3/ious7 What is not so o3/ious is the .act that the t6o particles can only 3e 4ept
apart i. they are in motion and this motion gi/es rise to a 4inetic energy 6hich must
3e positi/e and increases as the a/erage distance 3et6een the electron and the nucleus
decreases7 9o6e/er, it is a .undamental conse0uence o. the la6s o. classical and 0uantum
mechanics that the 4inetic (- + and potential (V + energies are al6ays in eactly the same
ratio 6hich, .or a system 6here the potential energy results .rom electrostatic attraction,
is V = 2 - 7 There.ore, .or any eigen/alue, n, o. the hydrogen atom the total energy
may 3e epressed as1
E
n
= -
n
+ V
n
= -
n
2-
n
= -
n
= V
n
,2
This relationship 3et6een - and V is 4no6n as the virial theorem7 Because o. it, 6e
can 3e sure that the negati/e potential energy o. the .orming hydrogen atom 6ill al6ays
eceed the positi/e 4inetic energy7
The epression .or the energy, '0uation (57#7#+, 6as Lrst deduced 3y SchroM dinger
and it pro/ided an eact, 0uantitati/e interpretation o. the Balmer .ormula7 ;aturally, all
the other lines in the hydrogen atom spectrum can also 3e Ltted to this .ormula (Bo
57#+7 As n increases n
2
increases /ery rapidly so that /alues o. E
n
3ecome closer and
closer together as they con/erge upon the /alue o. Kero7 We see the eperimental
e/idence .or this in the positions o. the lines in the spectra o. the hydrogen atom,
Digure B57#7# and Digure 27%7 Consider the Lyman series (Bo 57#+7 The energy re0uired
to raise the electron
.rom the energy le/el, n = #, to successi/ely higher le/els, n = 2 , * . . . increases, 3ut
3y a smaller amount, .or each increase in the higher 0uantum num3er7 Dinally, 6hen
n = the electron lea/es the atom 6hich is then said to ha/e 3een ionised7 Dor the
Lyman series this ionisation limit is .ound at #0$ ?--7? cm

#
6hich corresponds to a
6a/elength o. $#72 nm7 Since the Balmer series starts .rom the le/el n = 2 its ionisation
limit is correspondingly smaller at 2- *#$7* cm

#
or ,?*7- nm7
)1& THE 4AVE 6UNCTI2NS 26 THE HY3R2EN AT2M
The 6a/e.unctions o. the hydrogen atom are not easy to descri3e in a Cartesian co2
ordinate system o. three, mutually perpendicular aes7 The polar co2ordinate system 6ith
the nucleus at the origin is much more suita3le7 The polar system is descri3ed and the
t6o systems compared in Appendi -7
Though at Lrst sight the SchroM dinger e0uation .or the hydrogen atom loo4s
more .ormida3le in polar than in Cartesian co2ordinates, the apparent compleity
conceals the .act that a most important simpliLcation is possi3le7 The SchroM dinger
e0uation in the three /aria3les (r , # and $+ can 3e se%arated into three e0uations in each
o. 6hich only one o. the /aria3les occurs7 This ma4es the solution o. the e0uation and,
more importantly .rom our point o. /ie6, the interpretation o. the results much
simpler7 Because the e0uation can 3e separated, the total 6a/e.unction can 3e 6ritten
as a product o. three .unctions, each containing only one co2ordinate /aria3le, i7e71

nlm
!r # $" = R
nl
!r "
lm
!# "
m
!$"
!5.2.#" Where the su3scripts, n, l and m, indicate the 0uantum num3ers upon 6hich
that particular part o. the 6a/e .unction is .ound to depend7 'ach o. the .unctions R!r ",
!# "
$% The Structure and Spectroscopy o. the Atom
and !$" can 3e 6ritten in a /ery general .orm and these epressions, especially those
.or R!r " and !# ", are rather complicated7 9o6e/er, since 6e are interested only in a
comparati/ely small num3er o. them, 6e shall 6rite those out eplicitly (Appendi 5+
and re.er readers 6ho re0uire the general .ormulae to more ad/anced tets7
#2
A complete 6a/e .unction may 3e thought o. as an eact description o. a region
mapped out in space 6hich can 3e occupied 3y one electron, or 3y t6o electrons 6ith
opposite spins7 The pro3a3ility o. Lnding an electron at any point in that space is .ound
3y e/aluating the 6a/e.unction at that point and multiplying the result 3y its comple
con@ugate, i7e7

7 A. the product

is integrated Zsummed up\ o/er all the space


then the result is one 3ecause the 6a/e.unctions are normalised (Section ,75+7 Since 6e
no6 4no6 that 6e cannot thin4 o. the motion o. an electron in @ust the same 6ay as 6e
thin4 o. the motion o. a planet around the sun, the epression Qor3itG is not appropriate7
To ma4e the di..erence clear, 6hile at the same time reOecting the historical origins o.
the concept, the term or*ital has 3een coined and is no6 uni/ersally used to descri3e the
.unction 7
)1&1% T$e ra/ial ";n#tion< +
n<l
!r"
The .unction R
nl
!r " is 4no6n as the radial .unction 3ecause it contains only r , the
radial co2ordinate o. the polar co2ordinate system7 '0uation (5727#+ sho6s that it is
the only part o. the 6a/e .unction in 6hich the principal 0uantum num3er, n, occurs7
When 6e study the radial .unctions (Appendi 5+ 6e see that, apart .rom a normalising
.actor, they
consist o. an eponential .unction, ep!

Or ,na
0
"

ep!

=,2", and a polynomial in


r 7 Because its argument is negati/e, the eponential .actor ensures that the /alue o. the
6a/e .unction al6ays goes to Kero at large distances .rom the nucleus7 This means that
the s0uare o. the 6a/e .unction, and there.ore the pro3a3ility o. Lnding the electron, .alls
to Kero as 6e mo/e .urther .rom the centre o. the atom7 Dor the hydrogen atom O = #,
3ut i. the /alue o. O is larger, as it is .or eample in the helium (9e
+
+ ion, then the
eponential part o. the radial .unction .alls o.. much .aster than 6hen O = # reOecting
the 6ay in 6hich a larger nuclear charge holds the electron closer to the nucleus7 The
polynomial .actor causes the radial .unction to change sign as the /alue o. r changes
as sho6n in Digure 57#7 Those /alues o. r .or 6hich any particular radial .unction is
Kero are 4no6n as the radial nodes and 6e must note that such a node has the .orm o.
a sphere, en/eloping the 6hole atom and 6ith the nucleus at its centre7 ;ot all radial
.unctions ha/e nodes7 ". those listed in Appendi 5, R
20
!r " has one node at = = 2.0
(r = 2.0a
0
P a
0
= Bohr radius+, R
,#
!r " has one node at = = *.0 (r = ?.0a
0
+ and R
,0
!r "
has t6o nodes at = = #.2?% (r = #.$0a
0
+ and *7-,2 (r = -.#0a
0
+7 The num3er o. nodes
in an eigen.unction is intimately connected 6ith the corresponding eigen/alue and 6e
shall consider the su3@ect o. nodes again 6hen 6e ha/e descri3ed the ang1lar .unctions

lm
!# " and
m
!$"7
Apart .rom plots o. R!r " itsel., t6o other representations o. the radial .unction are
.re0uently used to illustrate the 6ay in 6hich the pro3a3ility o. Lnding an electron,
i7e7 the electron density, 3eha/es as the distance .rom the nucleus increases7 Since this
pro3a3ility is proportional to the s0uare o. the 6a/e .unction, graphs o. R
2
!r " against r are
.re0uently used .or this purpose7 Another .orm o. diagram is o3tained in the .ollo6ing
manner7 Since the sur.ace area o. a sphere o. radius r is *(r
2
, the /olume element
:
n
,
l
(
r
+


#
0
2
:
n
,
l
(
r
+
*
p
r
2
:
2
:
n
,
l
(
r
+
The Wa/e Dunctions o. the 9ydrogen Atom $$
570
275
070
072
07#
d2or3ital1 l = 2
n = ,
p2or3itals1 l = #
n = 2, ,
270
#75
#70
075
s2or3itals1 l = 0
n = #, 2, ,
070
07#
0 5 #0 #5 20
r (atomic units+
6ig;re )1% 9ydrogen2atom radial .unctions
070
0 5 #0 #5 20
r (atomic units+
%
-
2s
?
5
2p
#s
*
,
2
,d
,p
#
0
275
270
#75
#70
075
070
#70
,s
075
070
0 # 2 , * 0 5 #0 #5 20 25
r (atomic units+
6ig;re )1& 9ydrogen2atom radial density .unctions
enclosed 3et6een t6o spheres o. radii r and r + )r is *(r
2
)r 7 There.ore, the proportion
o. the hydrogen2atom electron 6hich lies 3et6een t6o such spheres, i7e7 at distance r
.rom the nucleus, is *(r
2
R
2
!r ")r 7 So a graph o. *(r
2
R
2
!r " against r is a
measure
o. the pro3a3ility o. Lnding an electron at a distance r .rom the nucleus (Digure 572+ 3ut
it can easily 3e misleading7 Because the .unction r
2
increases so rapidly 6ith increasing
r , the .unction *(r
2

R
2
!r " has one or more maima 6hich must 3e interpreted
6ith
care7 Dor eample, i. 6e 6ere a3le to stand at the hydrogen nucleus and eperience the
electron density o. the #s or3ital there in the 6ay in 6hich 6e eperience a .og 6e 6ould
Lnd that the .og 6as /ery dense at the nucleus7 As 6e 6al4ed a6ay .rom the nucleus the
thic4ness o. the .og 6ould decrease eponentially and 6e 6ould not see any increase in
the region o. r = a
0
6here the graph o. *(r
2
R
2
!r " against r sho6s a maimum7 The
maimum is a conse0uence o. the .actor r
2
7 ". course, 6here there are radial nodes
the
electron density must .all to Kero at these /alues o. r and increase again at greater r 7
)1&1& T$e ang;lar ";n#tions<
l<&
!# " an/
&
!$"
We might 6ell ha/e epected that an electron circulating around a nucleus 6ould ha/e
some or3ital angular momentum associated 6ith it, and this is indeed the case7 Durther, 6e
Ta?le )1% The possi3le 0uantum num3er com3inations .or the lo6er /alues o. n
n
#
l
0
m
0
n
2
l
0
m
0
#
# 0 +#
, 0 0 * 0 0
#
# 0 +#
#
# 0 +#
2 2 # 0 +# +2 2 2 # 0 +# +2
,
, 2 # 0 +# +2 +,
4no6 .rom Chapter * that 6e can al6ays characterise t6o aspects o. angular momentum,
the s0uare o. its total /alue and its B2component7 The 0uantum num3ers l and m do
@ust that and there.ore the 0uantum num3er .or the s0uare o. total angular momentum,
l, and the 0uantum num3er .or its B2component, m, are related 3y the epressionP m =
0

2 . . .

l7
]
But the detailed solution o. SchroM dingerGs e0uation .or the hydrogen
atom re/eals that the /alue o. l is itsel. restricted to integer /alues lying 3et6een 0
and (n #+7 An summary, the three spatial 0uantum num3ers can ta4e the .ollo6ing,
interrelated /alues1
n, the principal 0uantum num3er = # 2 , . . .
l, the or3ital angular momentum 0uantum num3er = 0 # 2 . . . !n #"
m, the 0uantum num3er .or the B2component o. the or3ital a7 m7 = 0 # 2 . . . l
The possi3le 0uantum num3er com3inations .or the lo6er /alues o. n, 6hich are the
only ones o. interest to us, are as sho6n in Ta3le 57#7
We Lnd it easier to remem3er the 0uantum num3ers and their signiLcance i. 6e use
a letter instead o. a num3er .or l, and .or reasons 6hich stretch 3ac4 into the history o.
atomic spectroscopy 6e use the letters s (sharp+, p (principal+, d (di..use+ and . (.undamen2
tal+ .or l = 0 # 2 and , respecti/ely7 There.ore, there are one s2or3ital, three p2or3itals,
L/e d2or3itals and se/en .2or3itals7
The .unctions
lm
!# "


m
!$" occur in many pro3lems 6hich, li4e the atom, ha/e
spherical symmetry7 They are 4no6n as the s%herical harmonics (Appendi 5+ and they
are .re0uently 6ritten as a single .unction, S
lm
!# $"7 The .orms o. these angular
.unctions are /ery important, especially so since the distri3ution o. electrons in space
around an atomic nucleus is a ma@or .actor 6hich a..ects the strength o. chemical 3onds
and the geometry o. molecules7 Allustrations o. the angular .unctions are there.ore /ery
important in the study o. chemical 3onding7
)1' !25AR 3IARAMS 26 THE ANU5AR 6UNCTI2NS
The most use.ul illustrations o. the angular parts o. the 6a/e.unctions o. the hydrogen
atom are o3tained 3y plotting them in polar co2ordinates as descri3ed in detail 3elo67
]
"ur notation here is not 0uite consistent7 A. 6e 6ere to .ollo6 the con/ention on angular momentum 0uantum num3ers
esta3lished in Chapter *, then i. l is the 0uantum num3er characterising total angular momentum, m
l
6ould 3e the .orm o. the
0uantum num3er .or the B2component o. that angular momentum7 The su3script is omitted to con.orm 6ith the usual notation
.or the atomic 0uantum num3ers since no con.usion can result .rom this and compleity in the notation is also reduced7
!olar <iagrams o. the Angular Dunctions #0#
2
Since the 0uantum num3ers m and l are related 3y l m +l, 6e must 3e care.ul to
com3ine only those .unctions
lm
!# " and
m
!$" .or 6hich this condition is
satisLed7
)1'1% T$e s9";n#tions
We start 6ith the s2.unctions o. 6hich there is only oneP
00
!# "
0
!$" =
#

!#,(
"7 Clearly, this .unction has no dependence upon either o. the t6o angular co2ordinates7 At
is
a .unction 6hich is eactly the same in all directions around the atom, i7e7 it is spherically
symmetrical7 We can represent it 3y dra6ing a spherical 3oundary sur.ace centred at the
nucleus and o. a radius such that a gi/en proportion o. the electron is enclosed 6ithin it,
$5 Y say7 All s2or3itals are represented 3y a sphere, 3ut the radius 6ill depend upon the
radial .unction 6ith 6hich the s2type angular .unction is com3ined in any particular case7
At the ris4 o. stating the o3/ious, it is emphasised that, a.ter the last radial node, the
electron density .alls o.. eponentially 6ith r so the 3oundary sur.ace is chosen ar3itrarily
and has no physical reality7
)1'1& T$e p9";n#tions
The %2.unctions,
#m
!# "
m
!$" S
#m
!# $", are o. three .orms depending upon
the /alue o. m, i7e7 m = #, 0 or +#7 Dor purposes o. illustration it is 3est to a/oid
using the comple .unctions 6hich contain ep!mi$" and to use the alternati/e
.unctions o.
cos!m$" and sin!m$"7 The di..erence 3et6een the t6o sets o. .unctions is that the comple
.unctions are eigen.unctions o. l

B
, the operator .or the B2component o. the or3ital angular
momentum, 6hereas the sine and cosine .unctions are not (see Chapters , and *+7 But,
i. 6e are not speciLcally interested in the or3ital angular momentum o. the electron 6e
loose nothing 3y this7 The simplest %2.unction is1
S
#0
=
#0
!# "
0
!$" =

!,,*(" cos!#
"
and to plot it 6e proceed as .ollo6s (Digure 57,+7
We dra6 the B2ais 6ith the nucleus, ;, at B = 0 and a radial co2ordinate .rom the
nucleus in a direction 6hich ma4es an angle # 6ith that ais7 :ecalling that # is the angle
3et6een the B2ais and the radial co2ordinate (r +, 6e mar4 o.. a length ;p e0ual to cos!#
" on the radial co2ordinate7 We repeat this process .or a num3er o. /alues o. # and 6e
note that, 3ecause o. the 6ay # is deLned, all angles in 6hich p has a positi/e B co2
ordinate
are in the range 0 # (,2 and cos!# " is there.ore positi/e7 All /alues o. # .or 6hich
p has a negati/e B co2ordinate (e7g7 pG in Digure 57,+ lie in the range (,2 # ( and
p
p
0
0
N

;
+
6ig;re )1' !lotting the angular .unction .or a p
B
2or3ital
# ,
#02 The Structure and Spectroscopy o. the Atom
cos!# " is there.ore negati/e7 When 6e ha/e mar4ed out su.Lcient points, on 3oth sides
o. the B2ais, 6e Lnd that p and pG descri3e t6o per.ect circles 6hich touch at N 7 This is
a %olar graph o. cos!# "7 Since the .unction S
#0
has no dependence upon the angle $, an
identical result 6ould 3e o3tained .or any plane 6hich contains the B2ais7 There.ore, in
three dimensions this representation o. S
#0
consists o. t6o spheres in contact and could
3e o3tained 3y rotating the t6o circles o. Digure 57, a3out the B2ais, i7e7 through all
possi3le /alues o. $7
The angular 6a/e.unction has a /alue o. Kero at #
=
$0

, i7e7 in the xy2plane, 6here


it changes phase7 This is an ang1lar node in the 6a/e .unction and all %2.unctions ha/e
one such planar angular node as 6e shall see 6hen 6e consider the other t6o .unctions1

, #

S
#c
=
2

sin!# "

(

cos!$" and S
#s
=
2

sin!# "

(

sin!$"
To plot these .unctions is slightly more complicated7 Dirst 6e L a /alue .or # and a
con/enient choice is $0

since sin!$0

" = #7 This choice o. # means that 6e are /arying


$ in the xy2plane and 6e plot it in eactly the same 6ay as 6e plotted # a3o/e7 At is
clear that .or S
#c
6e must o3tain the t6o circles in contact since 6e are again plotting a
cosine .unction7 That the result .or the sine .unction should also 3e the same, 3ut rotated
through $0

, may not 3e immediately o3/ious, 3ut it can 3e readily demonstrated 3y a


.e6 minutes o. plotting7
An Digure 57*, the point p
x
traces out cos!$" and the .unction S
#c
and p
y
traces out
sin!$" and the .unction S
#s
7 As 6ith the .unction S
#0
, the signs o. the t6o lo3es o.
the .unction are determined 3y the sign o. sin!$" or cos!$" in the appropriate 0uadrant7
:emem3er that $ is al6ays the angle 3et6een the x2ais and the radius /ector, N

p!p

"7
To o3tain the complete angular .unctions 6e must no6 consider the result o. /arying
#
o/er its range o. 0 to ( 7 The .unction in 0uestion is sin!# " 6hich .or any constant $ gi/es
t6o circles in contact in the plane deLned 3y the B2ais and the radius /ector N p!p

"7
The diameter o. each circle is N p!p

"7 Thus, i. 6e L a /alue o. $ at say, Kero, 6e
o3tain the polar plot o. S
#c
as t6o circles in contact in the xB2plane7 The t6o .unctions
R
p
y
+
.
p

.
F

;
+

Dor p

1 ;2p

= sin0 cos. Dor p
y
1 ;2p
y
= sin0 sin.
6ig;re )1( !lotting the angular .unctions .or p
x
2 and p
y
2or3itals
S
#c
and S
#s
turn out to 3e eactly li4e S
#0
consisting o. t6o spheres in contact 3ut
aligned along the x2 and y2aes respecti/ely7
Accordingly, these three angular .unctions are 4no6n as the p
x
, p
y
and p
B
.unctions7
At is important to note that a sum o. the s0uares o. the x2, y2 and B2.unctions has no
dependence upon # or $ and is there.ore spherically symmetrical7 Conse0uently, i. each %2
.unction is occupied 3y one or 3y t6o electrons the total electron distri3ution is spherically
symmetrical7 This is clearly the case .or the single s2.unction and it is also true o. the
L/e d 2.unctions, the se/en .2.unctions and so on7
A .urther point should 3e made 6ith regard to the .orms o. the s0uared .unctions7 A.
6e ma4e a polar plot o. S
2
#0
S
2
#c
or S
2
#s
6e o3tain results similar to those
o3tained a3o/e 3ut 6ith an important di..erenceP the t6o spheres 3ecome t6o pear2
shaped lo3es7 But the directional properties o. the .unctions remain 0uite unchanged and
either .orm o. plotting is suita3le .or a discussion o. the spatial characteristics o. %2
.unctions7
)1'1' T$e d9";n#tions
!olar diagrams o. the L/e d 2.unctions can 3e o3tained in the manner descri3ed a3o/e7
They are sho6n in Digure 5757 Again, .or purposes o. illustration the real sine and cosine
.unctions ha/e 3een chosen7 :eOecting their orientation 6ith respect to the Cartesian aes,
the d 2.unctions are named, d
xy
, d
xB
and d
yB
.or the three .unctions 6hich are directed
3et6een the aes indicated, and d
x
2

y
2 .or the .unction 6ith its lo3es lying along the

and y aes7 The .unction d


B
2

S
20
, is clearly di..erent and the reason .or this can 3e a
source o. di.Lculty7 An actual .act, it is not as di..erent .rom its companions as it appears
since it can 3e 6ritten as a com3ination o. t6o .unctions, d
B
2

x
2 and d
B
2

y
2 , 6hich
ha/e eactly the same .orm as the other .our d 2or3itals, i7e7 .our lo3es 6ith their aes at
right angles and lying in a plane7 We ha/e to 6rite the d
B
2
.unction in the .orm gi/en
3ecause
R N
+ +
N
F
+
+
d
y
F
+
d
K

N R
+
R
+
d
yK
+
d
K
2

+ +
F

2
y
2
6ig;re )1) d 2or3ital angular .unctions
i. 6e used the .unctions d
B
2

x
2 and d
B
2

y
2 6e 6ould ha/e si d 2.unctions 6hich 6ere
not mutually orthogonal and there.ore not independent o. each other7 To use such a
set o.
.unctions 6ould 3e li4e trying to plot a graph on a normal piece o. graph paper on 6hich
three, rather than t6o, aes had 3een dra6n7
The phases o. the d 2.unctions sho6 that they each ha/e t6o angular nodes 6hich, .or
all ecept the d
B
2
, consist o. t6o mutually perpendicular planes7 The angular nodes o. the
d
B
2
.unction ta4e the .orm o. t6o cones 6ith their apees at the nucleus7
The se/en .2.unctions are important in the chemistry o. the lanthanides and actinides,
3ut it 6ould ta4e us too .ar .rom the main theme o. this chapter to discuss them here7
<etails may 3e .ound in re.erence
,
7
)1( THE C2M!5ETE 2R8ITA5 4AVE 6UNCTI2NS
A complete 6a/e .unction,
nlm
!r # $", 6hich .orms a solution o. SchroM
dingerGs e0uation .or the hydrogen atom, is there.ore a product o. the three .unctions
R
nl
!r "

lm
!# "


m
!$" in 6hich 6e must recognise that the three 0uantum num3ers, n, l and
m
are not entirely independent o. each other7
The num3er o. nodes in the complete 6a/e .unction is the sum o. the radial and
angular nodes and rises 6ith increasing or3ital energy7 The total num3er o. nodes is
n # (Ta3le 572+7 But the actual .orm o. the angular .unctions does not change as the
0uantum num3er n increases, they simply reach out .urther .rom the nucleus, 3ecause o.
the increasing etension o. the radial .unction, and are intersected 3y an increasing num3er
o. radial nodes7 The occupation o. the energy le/els and the .orm o. the associated 6a/e
.unctions pro/ides the 4ey to understanding the chemical 3ond and molecular geometry7
These su3@ects are discussed in much more detail in Chapter ?7
)1) 2THER 2NE9E5ECTR2N AT2MS
Though hydrogen and its isotopes,
2
9 and
,
9, are the only elements 6hich ha/e
one electron in the neutral state, many positi/e ions 6hich ha/e @ust one electron are
4no6n and their spectra are .re0uently o3ser/ed in high2energy discharges 6here
electrons are
Ta?le )1& The nodes o. the hydrogen atom 6a/e .unctions
;um3er o. nodes ;um3er o. nodes
"r3ital "r3ital
n l radial angular total n l radial angular total
#s 0 0 0 *s , 0 ,
*p 2 # ,
2s # 0 # *d # 2 ,
2p 0 # # *. 0 , ,
,s 2 0 2 5s * 0 *
,p # # 2 5p , # *
,d 0 2 2 5d 2 2 *
5. # , *
5g 0 * *
# #0$ -#-7,5 9e
+
2 #0$ -2272?
, #0$ -2%7-2 Be
+++
* #0$ -,07?2
=
Atoms and Aons 6ith more than "ne 'lectron #05
Ta?le )1' 8alues o. the :yd3erg constant (R+ .or hydrogen and some
one2electron ions
AtomHion O R(cm

#
+ AtomHion O R(cm

#
+
9 # #0$ ?--75$
2
9 # #0$ -0-7*2
,
9
Li
++
stripped a6ay .rom atoms to .orm multiply charged ions7 The energy le/els and 6a/e
.unctions o. these one2electron ions are gi/en 3y the .ormulae .or the hydrogen atom
6ith the appropriate modiLcation o. the /alue o. the nuclear charge, O7 Ta3le 57, gi/es
the /alues o. the :yd3erg constant, R (see Bo 57#+, determined .rom the spectra o. 9,
9e
+
, Li
++
and Be
+++
7 The small change in the /alue o. R as 6e go .rom 9 to Be
+++
is due to the change in the mass o. the nucleus 6hich enters the .ormula .or the energy
le/els 6hen it is 6ritten in the strictly correct .orm1
E
n
= O
2
Te
*
,%h
2
?
0
2
n
2
in J or O
2
Te
*
,%ch
,
?
0
2
n
2
in cm

#
6here T = m
e
m
N
,!m
e
+ m
N
" is the reduced mass o. the electron, m
e
, and the nucleus,
m
N
7 Dor .urther discussion o. the reduced mass see Chapter #0 and Bo #07#7
This /ariation o. R 6ith nuclear mass is not simply an arcane theoretical point7 An #$,2,
the o3ser/ation o. a /ery 6ea4 line on the higher2energy side o. each o. the Balmer lines
6as important proo. o. the eistence o. a hydrogen isotope 6ith an atomic mass o. 27
)1* E5ECTR2N S!IN
Thus .ar, this account o. the structure o. the atom has 3een .ocused on the energy o.
the electron and its distri3ution in the space surrounding the atomic nucleus7 The angular
momenta in/ol/ed are or3ital angular momenta7 But immediately prior to SchroM
dingerGs pu3lication o. the ne6 6a/e mechanics, Goudsmit and =hlen3ec4 had proposed
that the nuances o. atomic spectral data, especially the Neeman e..ect (see Section
57##+, could 3est 3e interpreted on the assumption that the electron had an intrinsic
QspinG angular
momentum 6ith s
=
#
and m
s
#
7 At almost eactly the same time, !auli proposed his
2 2
eclusion rule (Section 57-72+ according to 6hich electrons 6ith opposed m
s
/alues 6ere
paired in the spatial or3itals descri3ed in the earlier part o. this chapter7 Thus, although
he did not eamine the electron spin .unctions, SchroM dinger 6as undou3tedly 6ell
a6are that spin 6as a property 6hich 6ould ha/e to .orm a part o. any comprehensi/e
theory o. atomic structure7 We also 4no6 that, in #$2%, the 6hole concept o. electron spin
6as placed on a much Lrmer .ooting 3y <iracGs relati/istic treatment o. the hydrogen
atom7 But 6e need only note that the property o. spin adds t6o more 0uantum num3ers,
s and m
s
, to those re0uired to .ully speci.y an electron in an atom7 The .urther
conse0uences o. electron spin 6ill 3e ta4en up in Section 57% on6ards7
)1+ AT2MS AN3 I2NS 4ITH M2RE THAN 2NE E5ECTR2N
The 9amiltonian operator .or a many2electron atom contains many terms7 'ach 4inetic2
energy term and the electron2nucleus attraction term in/ol/es only one electron7 These
#0? The Structure and Spectroscopy o. the Atom
one2electron terms present little di.Lculty to the 6ould23e calculator o. atomic structure7
But the terms descri3ing the mutual repulsion o. the electrons each in/ol/e t6o electrons
and though they are simple to 6rite do6n they are /ery di.Lcult to deal 6ith computation2
ally7 The pro3lem is this7 An the helium atom .or eample, ho6 can 6e 4no6 the energy
o. electron # 6hen 6e do not 4no6 ho6 electron 2 is distri3uted around the atomJ We
need to 4no6 the distri3ution o. electron 2 in order to calculate the energy o. the # I
2 inter2electronic repulsion7 There is no closed alge3raic solution o. this three+*ody
%ro*lem
(2 electrons + # nucleus+, neither in classical nor in 0uantum mechanics7 9o6e/er, there
is a 6ay .or6ard i. 6e are prepared to carry out a long cyclic calculation7 The procedure
is as .ollo6s, 6here 6e ta4e the lithium (Li+ atom as an eample7
)1+1% T$e sel"9#onsistent Bel/
We ha/e to determine a 6a/e .unction .or each o. the three lithium electrons7 Because
e/ery atom is spherically symmetrical, 6e 4no6 that the angular .unctions 6ill 3e the same
as those o. the hydrogen atom or3itals and that 6e shall there.ore ha/e 6a/e.unctions
6hich 6e may descri3e as #s and 2s, the Lrst containing t6o electrons and the second
one7 The pro3lem is to determine the appropriate radial .unctions 6hich are strongly
inOuenced 3y the presence o. the inter2electronic repulsion7 We start 3y guessing 6a/e
.unctions .or electrons 2 and , 3asing our guess upon 6hate/er in.ormation 6e ha/e .rom
eperiment or theory7 9a/ing done this 6e sol/e the SchroM dinger e0uation .or
electron
# mo/ing in the a/eraged electrostatic Leld o. the nucleus and electrons 2 and ,7 ;et
6e sol/e the SchroM dinger e0uation .or electron 2 using the guessed 6a/e .unction
.or electron , and the calculated 6a/e .unction .or electron #7 We no6 sol/e the e0uation
.or electron , using the 6a/e .unctions calculated .or electrons # and 27 The resulting three
6a/e.unctions and total electronic energy are not the Lnal ans6er since they are 3ased
upon the original guesses7 But they do pro/ide 3etter approimations to the true ans6ers
and i. 6e repeat the cycle o. calculations 6e can ma4e a .urther impro/ement in our
6a/e .unctions and energy7 A. the cyclic calculation is continued the changes in the 6a/e
.unctions and energy 3ecome smaller 6ith e/ery cycle until, 6ithin the limits o. accuracy
re0uired .or that particular calculation, there is no .urther change in them7 When this point
is reached the electronic 6a/e .unctions are said to 3e consistent 6ith the electrostatic
Leld .rom 6hich they 6ere calculated and 6hich the electrons themsel/es produce7 The
process is 4no6n as a self+consistent Celd (SCD+ calculation7 ;o6adays, computers ma4e
this tas4 rather easy, 3ut the Lrst calculations o. the type 6ere done the hard 6ay 3y the
9artrees, .ather and son, in the #$,0s7
]
;ota3le contri3utions to the su3@ect 6ere also
made 3y 8ladimir A7 Doc4 (#%$% I #$-*+ and 6a/e .unctions calculated 3y this
method are o.ten called 9artree I Doc4 .unctions7
)1+1& Ele#tron #orrelation
9o6e/er, e/en an SCD calculation does not pro/ide an eact radial 6a/e.unction7 Because
the electrons repel each other their motions are correlated, i7e7 they 4eep out o. each otherGs
]
The .ather (W9+ 6as a retired school teacher 6ith time to spare7 9is son, the physicist and mathematician <ouglas
:ayner 9artree (#%$- I #$5%+, set him to 6or4 on the long, demanding SCD calculations 6ith 6hich the .amily name
is no6 synonymous7
The 'lectronic States o. the Atom #0-
6ay, and this e..ect is not .ully allo6ed .or in the 9artree2Doc4 method 6hich assumes
that the electrons produce a static, spherical Leld and .ails to allo6 .or the dynamic e..ects
o. the inter2electronic repulsion 6hich is 4no6n as electron correlation7 This su3@ect 6ill
3e discussed .urther in Section ?7%7
)1+1' T$e perio/i# ta?le o" t$e elements
Today, SCD 6a/e .unctions are readily a/aila3le7 The angular .unctions are eactly the
same as those o. the hydrogen atom, 3ut the radial .unctions are not7 ;or can they
3e epressed as alge3raic .unctions o. r 3ut are gi/en as ta3les o. /alues7 Apart .rom
the increase o. energy 6hich the inter2electronic repulsion engenders, it also has the
conse0uence that the electrons can no longer 3e considered as indi/idual, independent
entities since their motions depend upon those o. their .ello6s, and /ice /ersa7 There.ore,
the 6a/e .unction and energy o. any one electron must depend upon the distri3utions and
hence the 6a/e .unctions o. all the other electrons in the atom, and one cannot truly spea4
o. the 6a/e .unction o. a single electronP the 6a/e .unction .or an atom is a .unction o.
the co2ordinates o. all the electrons7
;e/ertheless, chemists ha/e .ound it possi3le, and etremely use.ul, to thin4 in terms
o. indi/idual electrons occupying indi/idual or3itals in many2electron atoms and in terms
o. 3uilding up the atom (the a1f*a1 %rinci%le + 3y Llling the or3itals in order o. increasing
energy 6ith t6o spin2paired electrons (the Pa1li %rinci%le or excl1sion r1le+7 Thus 6e
ascri3e many o. the particular properties o. the transition metals and their ions to electrons
occupying ,d (Ti2Nn+, *d (Nr2Cd+ and 5d (9.29g+ or3itals and the electron 6hich is so
readily lost 3y the al4ali metal atoms is a 2s (lithium+, ,s (sodium+, *s (potassium+ . . .
electron7 The empty or partially Llled or3itals play a similarly use.ul role7 We en/isage
that the ,s electron lost 3y sodium enters the singly occupied ,p or3ital o. chlorine 6hen
the sodium and chlorine atoms com3ine to .orm sodium chloride7
An e/ery case these are electrons or or3itals in the outer reaches o. the particular atom,
i7e7 they are valence or3itals or valence electrons and ha/e the highest, or nearly the
highest, energy and /alue o. n7 Thus, a 0uantum2mechanical /ie6 o. the periodic ta3le
is an arrangement o. the elements in 6hich those ha/ing the same electronic structure
in their outermost, normally incomplete, shell are placed in columns7 The .act that the
structure o. the incomplete outer shell o. an element controls its reacti/ity, the num3er
o. chemical 3onds 6hich it .orms (/alency+ and the geometry o. the molecules o. 6hich
it .orms a part (see Chapter ?+ eplains the /ery similar chemical properties 6hich 6ere
the Lrst stimulus to the construction o. the ta3le7
)1, THE E5ECTR2NIC STATES 26 THE AT2M
Though indi/idual or3itals are /ery use.ul .or a 0ualitati/e or semi20uantitati/e description
o. the 6ay in 6hich a many2electron atom .orms chemical 3onds to other atoms, a more
eact description is re0uired i. 6e 6ish to account 0uantitati/ely .or the energetics o.
3ond .ormation or atomic spectroscopy7 Dor these purposes 6e re0uire a description in
6hich all the electrons in the atom are includedP i7e7 the electronic state o. a many2
electron atom must 3e characterised 3y means o. 0uantum num3ers that descri3e the total
2
#0% The Structure and Spectroscopy o. the Atom
angular momentum o. the atom7 The eact .orm in 6hich these 0uantum num3ers are
gi/en depends upon the atom in 0uestion .or reasons 6hich 6e shall disco/er 3elo67 We
start out 3y descri3ing a hydrogen2li4e or one2electron atom7
)1,1% T$e BAe @;ant;m n;m?ers o" a single ele#tron
These are the1
principal 0uantum num3er n
or3ital angular momentum 0uantum num3er l
0uantum num3er .or the B2component o. or3ital angular momentum m
l
spin angular momentum 0uantum num3er s
0uantum num3er .or the B2component o. the spin angular momentum m
s
At is clear that, 6ith the eception o. the Lrst, all these 0uantum num3ers characterise an
aspect o. the angular momentum o. the electron7 (The su3script l has 3een re2introduced
in m
l
in order to distinguish it .rom m
s
+7
)1,1& Q;ant;m n;m?ers "or t$e man09ele#tron atom
As noted a3o/e, the proper description o. a many2electron atom must 3e a description
6hich includes all the electrons7 Since the spherical symmetry o. the atom is maintained
as more electrons are added, the angular momentum 0uantum num3ers remain /alid and
are central to this description7 An analogy 6ith those 6hich re.er to indi/idual electrons,
6e introduce .our ne6 0uantum num3ers, L, 5
L
, S and 5
S
, 6hich descri3e the or3ital
and spin angular momenta o. all the electrons, collecti/ely7 'tending the notation, lo6er
case letters .or one electron, upper case letters .or t6o or more electrons, 6e say that
atoms 6ith /alues o. L = 0 # 2 , . . . are in S P E 9 . . .
states7
The /alue o. S (total spin 0uantum num3er+ is important 3ecause it characterises the
multiplicity o. the spin state, i7e7 the num3er o. 5
S
/alues, 6hich is 2S + # (Section *7*+,
and the multiplicity is normally added to the sym3ol .or the state as a le.t superscript, e7g7
.or S =
#
and L = 2 6e ha/e a
2
< state (spo4en dou3let <+, .or S = 2 and L = # 6e
ha/e a
5
! state (0uintet !+7 The /alues o. 5
S
and 5
L
are not usually speciLed7 Sym3ols
such as
2
< and
5
! used to descri3e the states o. atoms are 4no6n as term sym*ols and
in the net section a method o. Lnding the possi3le L and S /alues .or a particular
arrangement o. electrons in or3itals, i7e7 a conCg1ration, is descri3ed7
]
)1,1' T$e assignment o" term s0m?ols
Gi/en a particular atomic conLguration, i7e7 an assignment o. electrons to hydrogen2li4e
atomic or3itals, the determination o. the possi3le states or terms o. the atom is 0uite
]
At is most un.ortunate that in this notation, 6hich is almost #00 years old and there.ore 0uite impossi3le to change, the
sym3ol S stands .or t6o completely di..erent angular momentum properties7 Dortunately, the possi3ilities o. error due to a
con.usion 3et6een the t6o 0uantities represented 3y S are /ery .e67
2
straight.or6ard7 Dirstly 6e recognise that i. e/ery one o. the n
2
or3itals corresponding to
a particular principal 0uantum num3er, n, is dou3ly occupied, all components o. spin and
or3ital angular momenta cancel to gi/e a total angular momentum o. Kero7 There.ore, all
such closed shells can 3e ignored in the determination o. term sym3ols7 The treatment
o. the partially Llled shells is 3est carried out 3y constructing a ta3le as illustrated in
the .ollo6ing eample in 6hich the conLguration p
2
is analysed7 We concentrate our
attention upon the possi3le B2components o. or3ital and spin angular momenta, since
these can 3e simply added 3ecause they are all aligned along B, and .or the p
2
pro3lem
the maimum 5
L
= m
l#
+ m
l2
/alue is # + # = 27 Similarly, the maimum /alue o.
5
S
is
#
+
#
=
#7 Since 6e 4no6 (Section *7*+ that the B2components, 5
U
, o. angular
2 2
momentum, U, al6ays ta4e all /alues 3et6een
+
U and

U in unit steps, our 5


L
/alues
must run .rom
+
2 to

27 Similarly, our 5
S
/alues must 3e
+
#, 0 and

#, and 6e
arrange these data as sho6n in Ta3le 57*7 The sym3ol in 3rac4ets gi/es the m
l
and m
s
o. electron # and electron 2, i7e7 (m
l#
m
s#
P m
l2
m
s2
+, 6hich add to gi/e the 5
L
and 5
S
/alues at the side and head o. the ta3le7 There is no entry in the position 5
L
= +2
and 5
S
= +# 3ecause this could only 3e achie/ed i. 3oth electrons occupied the same p
or3ital (m
l
= +#+ and had the same spin (m
s
= +
#
+ 6hich is .or3idden 3y the !auli
principle7 The 3rac4eted sym3ols are the possi3le microstates o. the system and 6e can
readily chec4 that 6e ha/e .ound the correct num3er o. them1 #57 A p electron can ha/e
si com3inations o. the 0uantum num3ers m
l
and m
s
7 There.ore, 6e ha/e a choice o. si
possi3ilities .or our Lrst electron7 Since no t6o electrons can ha/e the same com3ination
o. the L/e 0uantum num3ers, 6e ha/e only L/e possi3ilities .or the second electron
ma4ing ? 5 = ,0 possi3ilities in total7 But electrons are indistinguisha3le so that, .or
eample, !+# +
#
P 0
#
" !0
#
P +# +
#
" and there are there.ore ?
5
= #5 possi3le
2 2 2 2 2
microstates o. the system7
To Lnd the terms o. p
2
6e Lrst .ocus our attention upon the entry in the ta3le 6hich
has the highest 5
L
/alue and, i. there are more than one o. these, upon that 6hich has
3oth the highest 5
L
and the highest 5
S
/alue7 An Ta3le 57* the entry 6ith the highest 5
L
/alue is (
+
#
+
#
P
+
#

#
+7 The .act that there is a microstate 6ith an 5
L
/alue o.
+
2
2 2
tells us immediately that it must 3e accompanied .our other microstates 6ith 5
L
/alues
o. +#, 0, # and 2 and that the L/e together .orm a state 6ith L = 2, i7e7 a < state7
The same reasoning tells us that since 5
S
= 0 there are no other spin components o. this
state 6hich has S = 0 and 2S + # = #, i7e7 6e ha/e .ound a
#
< term7 We there.ore tic4
o.. one micro state in each 3o ha/ing 5
S
= 0 and 5
L
= +2 . . . 27 We do not need
Ta?le )1( The microstates o. the electron conLguration p
2
5
S
+# 0 #
+
2 (
+
#
+
#
P
+
#

#
+
2 2
+
# (
+
#
+
#
P 0
+
#
+ (
+
#
+
#
P 0

#
+ (
+
#

#
P 0
+
#
+ (
+
#

#
P 0

#
+
2 2 2 2 2 2 2 2
5
L
0 (
+
#
+
#
P

#
+
#
+ (
+
#
+
#
P

#

#
+ (
+
#

#
P

#
+
#
+ (
+
#

#
P

#

#
+
2 2 2 2 2 2 2 2
(0
+
#
P 0

#
+
2 2

# (

#
+
#
P 0
+
#
+ (

#
+
#
P 0

#
+ (

#

#
P 0
+
#
+ (

#

#
P 0

#
+
2 2 2 2 2 2 2 2

2 (

#
+
#
P

#

#
+
2 2
,
!
0
,
!
#
,
!
2
to identi.y 6hich o. the microstates, in a group 6ith more than one, 3elongs to
#
<, the
tic4ing process is merely one o. Q4eeping accountG7
We no6 identi.y the microstate among those remaining 6hich has the highest 5
L
and
5
S
/aluesP it is (
+
#
+
#
P 0
+
#
+7 Since it has 5
L = +
# and 5
S = +
# this microstate
2 2
must 3e one o. the nine 6hich .orm a
,
! term and 6e tic4 o.. microstates in Ta3le 57*
accordingly7 A single microstate 6ith 5
S
= 0 and 5
L
= 0 remains and this must 3e the
single component o. a
#
S term7 So our result is that the conLguration p
2
gi/es rise to three
termsP
#
< (5 components+,
,
! ($ components+ and
#
S !# component" = #5 components
in total = num3er o. microstates in Ta3le 57*7
At should 3e admitted here that the a3o/e method o. determining the terms o. a particular
conLguration is more /alua3le as an illustration o. the meaning o. a term sym3ol and o.
the su3tle 6ay in 6hich the spin and or3ital angular momenta o. t6o electrons com3ine
than it is as a practical research tool7 A conLguration 6ith se/eral . electrons, such as 6e
Lnd in the rare earths, is e..ecti/ely impossi3le to analyse 6ith this method (e7g7 .
*
has
#00# microstatesU+ and some etremely sophisticated mathematical techni0ues ha/e 3een
de/eloped to deal 6ith this type o. pro3lem7 'ach term in a conLguration has a di..erent
energy 3ecause o. the di..erent contri3utions .rom inter2electronic repulsion in each one7
But the !2S + #"!2L + #" components 6ithin each term ha/e almost eactly the same
energy7 An .act they 6ould 3e degenerate 6ere it not .or an e..ect 4no6n as s%in+or*it
co1%ling 6hich splits each term into a num3er o. le/els o. di..erent energy, as sho6n in
Section 57$7
)1,1( Term energies an/ H;n/s r;les
As 6e ha/e seen, a single electron conLguration can gi/e rise to se/eral terms and, in
general, all o. these ha/e di..erent energies 3ecause o. the di..erent contri3utions .rom
the inter2electronic repulsion in each one7 Ta3le 575 gi/es the energies o. some eamples
o. the conLguration np
2
7 (The energy o. the
,
!
0
state has 3een ar3itrarily set to Kero7+ The
energies o. the
,
! states are not all e0ual 3ecause o. spin2or3it coupling (see Section 57$+,
so a 6eighted mean energy is gi/en in the .ourth column o. the ta3le7
The electron spin plays an important role in determining the inter2electronic repulsion
and it does so in a rather su3tle 6ay, the details o. 6hich depend upon the connection
3et6een the electron spin and spatial 6a/e .unctions and the !auli principle7 This is
eplored in detail in Chapter ##7 9ere it 6ill 3e su.Lcient to recognise that, in order to
con.orm 6ith the !auli principle, di..erent electron spin .unctions must 3e com3ined 6ith
di..erent electron spatial .unctions7 Thus, since the inter2electronic repulsion is directly
determined 3y the spatial distri3ution o. the electrons, the energies o. the /arious terms
are di..erent7 This .act 6as noted in #$2- 3y Driederich 9und (#%$? I +, largely as a
result
Ta?le )1) The energies (in e8+ o. the terms arising .rom the conLguration np
2
,
!(mean+
#
<
2
#
S
0
Ge *p
2
070 070?$# 07#-*% 07#20# 07%%,* 2702$,
Sn 5p
2
070 0720$% 07*250 07,0?0 #70?-$ 27#2-$
!3 ?p
2
070 07$?$5 #7,205 #705?% 27??05 ,70$55
Spin2"r3it Coupling ###
o. eperimental studies o. atomic spectra7 "n the 3asis o. his o3ser/ations 9und proposed
t6o rules .or e0ui/alent electrons1
#7 The terms o. highest multiplicity lie lo6est in energy7
27 A. t6o terms ha/e the same multiplicity the lo6est is that 6ith the greatest /alue o. L7
The data in Ta3le 575 illustrate 9undGs rules7 The
,
! states are the lo6est and one o.
them,
,
!
0
, is the ground state7 Also,
#
< is lo6er than
#
S7
)1- S!IN92R8IT C2U!5IN
The origin o. spin2or3it coupling is easy to understand7 To an electron or3iting an atomic
nucleus the nucleus appears to 3e an or3iting positi/e charge7 This or3iting charge gen2
erates an electric current 6hich, in turn, produces a magnetic Leld at the electron7 This
magnetic Leld interacts 6ith the magnetic Leld due to the spin o. the electron and the
energy o. interaction is 4no6n as the spin2or3it coupling energy7 Theory sho6s that the
e..ect is proportional to O
*
, 6here N is the nuclear charge, and it there.ore increases
/ery steeply 6ith increase in atomic num3er7 The coupling o. the spin and or3ital angu2
lar momenta o. an electron, 6hich results .rom this interaction, mies those 0uantities
together so that, especially .or hea/y atoms, it is possi3le to spea4 o. L and S only as
approimate 0uantum num3ersP the only eact angular momentum 0uantum num3er 3eing
Q , 6hich is a com3ination o. the t6o7 There are t6o 6ays o. determining Q , one o. 6hich
is appropriate .or light atoms and one .or hea/y7
)1-1% R;ssell I Sa;n/ers or L' #o;pling
Dor light atoms the /alues o. Q can 3e o3tained 3y adding together the /alues o. L
and S .or the total or3ital and spin angular momenta o. the electrons determined as in
Section 57%7,7 We add the angular momenta using the .ormula (Section *7?+1
Q = L + S L + S # L + S 2 . . . |L S|
The /alues o. Q are 6ritten as a right su3script on the term sym3ol, e7g7 .or p
2
1
#
< !S = 0 L = 2" ===
#
<
2
,
! !S = # L = #" ===
,
!
2

,
!
#
and
,
!
0
#
S !S = 0 L = 0" ===
#
S
0
'ach state ha/ing a particular /alue o. Q has 2Q + # components 6ith 5
Q
/alues run2
ning .rom +Q to Q and in the a3sence o. a magnetic Leld, vide infra, all are degenerate7
Thus, as a result o. spin2or3it coupling, a
,
! term 6hich 6as nine2.old degenerate, is split
into a L/e2.old degenerate
,
!
2
, a three2.old degenerate
,
!
#
and a singly degenerate
,
!
0
term7 The L/e2.old degeneracy o. the
#
< term is not remo/ed and the
#
S
0
term has
only one component7
When 6e .ormulate spin2or3it coupling in this 6ay 6e call it LS coupling 3ecause 6e
com3ine /alues o. L and S to gi/e Q 7 At is also 4no6n as :ussell2Saunders coupling a.ter
##2 The Structure and Spectroscopy o. the Atom
t6o astronomers 6ho Lrst used it to interpret the atomic spectra o. stars in #$25, 3e.ore
the ad/ent o. 0uantum mechanics as 6e 4no6 it7
Thus, in order to o3tain a model o. the electronic structure o. a light, many2electron
atom, 6e 3uild up our description in three stages7
#7 We Lrst thin4 o. a many2electron atom as 3eing composed o. a num3er o. electrons
each mo/ing in an or3ital characterised 3y 0uantum num3ers n l m
l
s and m
s
7 We
recognise that the radial parts o. these or3itals 6ill depend upon the charge on the
nucleus and that the electrons 6ith lo6 /alues o. n 6ill there.ore 3e /ery close to
the nucleus 6hile electrons in or3itals 6ith higher /alues o. n 6ill reach out much
.urther into the space surrounding the atom7 Those 6ith the highest /alue o. n are the
/alence electrons 6hich are the most important in the .ormation o. chemical 3onds
and in atomic spectroscopy7
27 ;et 6e ta4e account o. the .act that, although the indi/idual n /alues are unchanged,
the detailed .orms o. the radial .unctions 6ill 3e changed 3y the inter2electronic repul2
sion7 Durthermore, 3ecause the electronic motions are correlated and 3ecause 6e cannot
distinguish 3et6een indi/idual electrons in a many2electron system, the indi/idual /al2
ues o. l and s are no longer meaning.ul and must 3e replaced 3y L and S 6hich
descri3e the or3ital and spin angular momenta o. the electrons as a 6hole7
,7 Dinally, 6e recognise that the e..ect o. spin2or3it coupling re0uires that 6e com3ine
L and S to gi/e a total angular momentum 0uantum num3er Q 7
At should 3e noted that the three steps a3o/e are associated 6ith three physical e..ects
o. diminishing energy7 An step # 6e ha/e the 4inetic and potential energies o. the electrons
mo/ing in the Leld o. the charged nucleus7 An the second step, 6e add the smaller energy
due to the inter2electronic repulsion7 An step , 6e add the spin2or3it coupling energy
6hich, .or atoms 6ith atomic num3ers less than 20, is e/en smaller7 When carried out
6ith proper mathematical precision, this process o. eamining the largest contri3ution to
the energy Lrst and then adding in the e..ects o. .urther, smaller energy terms in order o.
decreasing energy is called %ert1r*ation theory (Appendi *+7 At has 3een 4no6n since the
time o. Lord :ayleigh (#%*2 I #$#$+ and has etensi/e uses in 3oth classical and
0uantum mechanics7 At is important that the energy contri3utions are ta4en in order o.
decreasing magnitude and in the case o. /ery hea/y atoms the spin or3it coupling,
6hich goes as O
*
, eceeds the inter2electronic repulsion and must there.ore 3e
considered Lrst7
)1-1& ,, #o;pling
Since 6e re0uire to consider spin2or3it coupling 3e.ore inter2electronic repulsion .or atoms
in the later ro6s o. the periodic ta3le, in step 2 6e Lrst com3ine the /alues o. l and s,
adding the angular momentum 0uantum num3ers as descri3ed in Section *7?, to ma4e a
& /alue .or each indi/idual electron, i7e7 in the case o. p
2
1
.or each p electron l
=
# and s
=
#
===
&
p
=
,
and
#
2 2 2
;o6, in step ,, 6e must add the & /alues together to gi/e Q .or the 6hole atom7 Where
6e ha/e t6o ine0ui/alent electrons, e7g7 p
#
d
#
, then 6e simply com3ine all the
possi2 3le m
&
/alues .or the d2electron 6ith all those .or the p2electron, in pairs7 But
in the
, # # , # #
2 2

2

2 2

2

2 # 0 2 #

0
#
# 0
2
0
#
# 2
0

p
p
&
2
&
Spin2"r3it Coupling ##,
Ta?le )1* The 5
Q
/alues o. the microstates o. np
2
in && coupling
p
,
p
#
2 2
,
2
#
, 2
2
#

2
,

2
#
# 2
2
#

2
case o. t6o e0ui/alent electrons, e7g7 p
2
.or 6hich 6e determined the term sym3ols in
Section 57%7,, 6e eperience again the pro3lem that 6e had in constructing Ta3le 57*,
i7e7 6e must 3e a6are o. the !auli principle7 Dor the conLguration np
2
6e ha/e possi2
3le & /alues o. #
+
#
=
,
and #

#
=
#
and *
+
2
=
? possi3le m
&
/alues7 A s0uare,
2 2 2 2
? ? array o. all possi3le com3inations o. t6o m
&
/alues (Ta3le 57?+, 6ould gi/e ,?
microstates7 But there can only 3e ?

5
=
#5 states .or t6o p2electrons and the .ol2
lo6ing states must 3e re@ected1 all si states on the diagonal o. the array, 3ecause i.
t6o electrons in the same shell ha/e the same & /alue and the same m
&
/alue
then they are identical and must 3e occupying the same atomic 6a/e .unction 6ith the
same spin7 This is contrary to !auliGs principle7 Durther, since electrons are
indistinguisha3le, an o..2diagonal array element o. the .orm Z& m
&
(#+P &

m

(2+\
cannot 3e distinguished .rom its Qmirror2imageG across the diagonal Z&

m

(#+P & m
&
(2+\7 These t6o microstates
together
{
Z& m
&
!#"P &

m

!2"\

Z&

m

!#"P & m
&
!2"\
}
,

2 descri3e a state o. the system so


& &
that #5 o. the ,0 o..2diagonal microstates must 3e neglected in the state2counting process7
We ar3itrarily choose the #5 microstates 3elo6 the diagonal lea/ing ,? ? #5 = #5
microstates (Ta3le 57?+7 Dollo6ing our usual method, 6e no6 start 6ith the largest 5
Q
/alue, remo/e the remaining 2Q 5
Q
/alues associated 6ith it and repeat the process until
all 5
Q
/alues ha/e 3een accounted .or7 The p

,
p
,
triangle gi/es Q = 2 and 0, the p

,
p
# 2 2 2 2
rectangle gi/es Q = 2 and # and the p

#
p
#
triangle gi/es Q = 07 The total num3er o. states
2 2
calculated .rom these Q /alues is 5 + # + 5 + , + # = #5 conLrming the correctness o.
our 6or4ing7
)1-1' Interme/iate #o;pling
We ha/e noted a3o/e that LS or :ussell2Saunders coupling applies /ery 6ell to light
atoms and && coupling to hea/y atoms7 But 6hat a3out atoms o. intermediate mass, or N
/alueP there is no sudden change .rom LS to && couplingJ This is a pro3lem typical o.
the physical sciences and especially so o. 0uantum mechanics7 We ha/e solutions .or the
etremes o. our pro3lem 3ut not .or the intermediate region .or 6hich, in .act, no simple
solution is possi3le7 The root o. our di.Lculty lies in the application o. the steps o. the
pertur3ation theory outlined in Section 57$7#7 At is important to ta4e the larger terms 3e.ore
'
n
e
r
g
y

(
a
r
3
i
t
r
a
r
y

u
n
i
t
s
+
'
n
e
r
g
y

(
a
r
3
i
t
r
a
r
y

u
n
i
t
s
+
the smaller ones and .or light atoms this means ta4ing inter2electronic repulsion 3e.ore
spin2or3it coupling7 Dor hea/y atoms the order must 3e re/ersed7 Dor the intermediate
case the only correct approach is to ta4e inter2electronic repulsion and spin2or3it coupling
together at the same time, since they are o. compara3le magnitudes7 This cannot 3e done
in as simple a manner as in the eamples descri3ed a3o/e, e/en .or t6o electrons7 A
more complicated calculation is re0uired (see Bo 572+7 But 6ith the help o. the digital
computer the calculation o. the terms or electronic energy states o. atoms presents little
di.Lculty today7
Dor systems 6ith a small num3er o. electrons such as np
2
a correlation diagram sho62
ing the transition .rom LS, through the intermediate region, to && coupling is use.ul in the
assignment o. atomic spectra7 Digure 57?, calculated 6ith data .rom Condon and Shortley,
*
sho6s the np
2
correlation diagram7 H is proportional to the ratio o. the spin2or3it cou2
pling to inter2electronic repulsion so that the Kero on the le.t2hand end o. the a3scissa
represents pure LS coupling 6hile the Kero on the right represents pure &&7 The assign2
ment o. the n%
2
electronic states o. germanium (n
=
*+, tin (n
=
5+ and lead (n
=
?+ is
also included and the mo/e .rom LS to && coupling 6ith increase o. nuclear charge is
/ery clear7 The energy scales at the t6o ends o. the diagram are not e0ual, they ha/e
3een modiLed so that the total spread o. the states is the sameP #5 energy units7 The
details o. this modiLcation
*
need not concern us here7 9o6e/er, 6e should not lea/e
this su3@ect 6ithout remar4ing upon the /alue o. the correlation diagram in chemistry7
Because, as chemists, 6e are o.ten interested in groups o. similar species, e7g7 the aro2
matic hydrocar3ons or the atoms in a particular ro6 or column o. the periodic ta3le,
6e 6ish to understand ho6 the properties o. a particular group o. atoms or molecules
/ary as their .undamental physical properties /ary across the group7 This in.ormation
can sometimes 3e displayed in diagrammatic .orm, the most 6ell24no6n eample o. this
3eing the periodic ta3le itsel.7 But there are many other important eamples in physics
and chemistry7
LS
#0
#
S
0
& &
& & Q
#0
,H2 ,H2 0
5 Ge *p
2
Sn 5p
2
!3 ?p
2
#
<
2
0
,
!
2
5 #
0
5
,H2 ,H2 2
0
,H2 #H2 2
,H2 #H2 #
5
#0
070 075
c
#70 075
#Hc
#H2 #H2 0
070
#0
:eprinted 6ith permission, '787Condon and G797 Shortley, a-he -heory of Atomic S%ectraa,
#$,5, Cam3ridge =ni/ersity !ress7
6ig;re )1* Spin2or3it coupling in np
2
Selection :ules in Atomic Spectroscopy ##5
)1-1( Inter9ele#troni# spin9or?it #o;pling
The or3ital magnetic moment o. an electron can also interact 6ith the spin magnetic
moment o. another electron, and /ice /ersa7 9o6e/er, the energies concerned are /ery
small compared 6ith those due to the intra2electronic e..ects 6hich 6e ha/e descri3ed
a3o/e and they are usually neglected7
)1%. SE5ECTI2N RU5ES IN AT2MIC S!ECTR2SC2!Y
(<)<*
An many places in this chapter re.erence has 3een made to the in.ormation 6hich atomic
spectroscopy pro/ides a3out atomic structure7 But 6e must not thin4 that e/ery energy
state o. the atom can 3e reached .rom e/ery other state 3y the emission or a3sorption o.
radiation7 The process is su3@ect to restrictions, 4no6n as selection rules, 6hich result .rom
the re0uirements that energy and angular momentum must 3e conser/ed7 At is precisely
3ecause these restrictions eist that so much detailed in.ormation has 3een o3tained7 The
conser/ation o. energy is em3odied in the Bohr2'instein selection rule1
E = h>
The change in energy o. the atom must 3e eactly e0ual to the energy o. the photon
a3sor3ed or emitted7
)1%.1% Ang;lar moment;m
The photon o. electric dipole radiation has an angular momentum characterised 3y the
angular momentum 0uantum num3er #, 3ut 6ith only t6o B2components, +# and #,
parallel and antiparallel to the direction o. propagation7 (This su3@ect is discussed in more
detail in Section %7* and the treatment here 6ill there.ore 3e 3rie.7+ Thus, since angular
momentum is conser/ed, in one2electron atoms atomic transitions 3et6een atomic or3itals
6ith angular momentum 0uantum num3ers l and l

must 3e such that l

=
l
+
#, l or l

#,
and the B2component o. the angular momentum must also 3e conser/ed7 The electron spin
does not interact 6ith the oscillating electric Leld o. the radiation so it is not changed7
(;ote ho6e/er, that the spin does interact 6ith the radiationGs magnetic Leld and this
interaction is /ery important in magnetic resonance spectroscopy and in magnetic dipole
transitions, Section 57#07#727+
An summary, the selection rules .or dipolar radiation in one2electron atoms are1
#7 s = 0
27 l = 0, #, 3ut l = 0 is .or3idden 3y parity (see Section 57#072+
,7 m
l
=
#
There is no restriction on the change in the /alue o. the principal 0uantum num3er,
n, 6hich accounts .or series o. lines such as the Balmer series7
When 6e consider many2electron atoms the position 3ecomes more complicated and,
in general, the interaction o. spin and or3ital angular momenta must 3e considered7 An the
limit o. pure LS coupling 6e ha/e .or electric dipole radiation1
#7 S = 0
27 L
=
0,

#, 3ut L
=
L

=
0 is .or3idden
##? The Structure and Spectroscopy o. the Atom
,7 5
L
= #
*7 Q
=
0,

#, 3ut Q
=
Q

=
0 is .or3idden
As 6e mo/e a6ay .rom LS coupling, into the intermediate region and to6ards &&
coupling the 0uantum num3ers S and L 3ecome increasingly poorly deLned and the
selection rules progressi/ely less deLniti/e7 Selection rules epressed in terms o. changes
o. state 0uantum num3ers are the results o. application o. angular2momentum theory to the
coupling 3et6een atom and radiation7
*5
They apply only to idealised situations, e7g7 %1re
LS coupling7 A. eact in.ormation on a particular transition is re0uired the detailed 6a/e
.unctions .or the states in 0uestion must 3e determined and the transition moment integral
e/aluated7 This su3@ect is discussed in much more detail in Bo 5727 Sections %7- and ##7-
and Appendi $ also contain rele/ant in.ormation7
-./0././ Electric 1uadrupole transitions
An some atoms and ions, e7g7 "
2
+
, /ery 6ea4 transitions 6hich are .or3idden 3y the selec2
tion rules descri3ed a3o/e, 3ut not induced 3y spin2or3it coupling, ha/e 3een o3ser/ed7
These transitions satis.y selection rules in 6hich the photon in/ol/ed appears to carry
t6o units o. angular and they are ascri3ed to 0uadrupolar photons7
*5
9o6e/er, photons
in a 3eam o. light ha/e not, to this authorGs 4no6ledge, 3een sho6n to carry t6o 0uanta
o. angular momentumP in contrast to the case o. a 3eam o. circularly polarised light, the
photons o. 6hich ha/e 3een sho6n 3y Beth
-
to carry hH2( units o. angular momentum
each7 At 6ould appear that a deLniti/e analysis o. the conser/ation o. angular momentum
in 0uadrupolar transitions is not yet a/aila3le7
-./0./.2 "agnetic dipole transitions
The magnetic Lelds arising .rom the or3ital and spin angular momentum o. the electron
can also interact 6ith the magnetic Leld o. an impinging photon7 The transitions 6hich
result are 4no6n as magnetic dipole transitions7 They are o. the order o. #0

-
times
6ea4er than electric dipole transitions7
)1%.1& !arit0
An order to understand the concept o. parity it is 3est i. 6e Lrst consider a 6a/e.unction o.
an atom, !x y B", and per.orm upon it the operation o. multiplying the three Cartesian
co2ordinates 3y #7 We call this operation the parity operation and it can 3e represented
3y the e0uation1
6here



!x y B"
===
!

B"
is the parity operator7
A. 6e per.orm this operation on the hydrogen #s or3ital (Appendi 5+ then1
#


#s
=

(
,
O

2
a
0
#

ep!

=,2"
=
(
,
O

2
a
0
ep!=,2"
#

l
B l B
and the .unction is unchanged 3ecause = is proportional to the positi/e s0uare root o.
(x
2
+
y
2
+
B
2
+7 Conse0uently,
#s
does not change sign 6hen the signs o. the Cartesian
co2ordinates are changed and is there.ore said to 3e even7 All s or3itals are e/en7 But i.
6e apply the parity operator to the 2p
B
6a/e .unction then1


2pB
=


2
5
#

O

2
2(
a
B ep!

=,2"
=

5
O

2
a
B ep!=,2"

0 2 2( 0
and 6e Lnd that the .unction changes its sign (3ecause

B = B+7 At is odd as are all
p .unctions7 But note that the 6a/e .unction is still an eigen.unction o. the 9amiltonian
operator 6ith the same energy eigen/alue as 3e.ore7
All atomic 6a/e .unctions can 3e classiLed into t6o groups7 Those 6hich are unchanged
under the parity operation, the s, d, g, . . . .unctions, are said to 3e e/en and they are
sometimes denoted 3y g (.rom the German QgeradeG = e/en+7 Dunctions 6hich change sign
under the parity operation, the p, ., h, . . . .unctions, are said to 3e odd and denoted 3y u
(.rom the German QungeradeG+7 The rules .or com3ining parities are @ust the same as those
.or multiplying the num3ers +# and #7 Thus, i. t6o .unctions o. the same parity, e/en
or odd, are com3ined the result is a .unction o. e/en parity, 6hereas i. t6o .unctions o.
di..erent parities are com3ined the resulting .unction is o. odd parity7
'lectric 0uadrupole and magnetic dipole photons, Sections 57#07#7# and 57#07#72, are
o. e/en parity7 But the great ma@ority o. eperimental o3ser/ations in atomic spectroscopy
in/ol/e dipolar photons 6hich are o. odd (u+ parity7 This means that the initial and Lnal
states o. a transition must 3e o. opposite parity so that, (parity o. initial state+ u = (parity
o. Lnal state", and parity is conser/ed7 Alternati/ely 6e may argue (Appendi $+ that,
since the dipolar photon is o. u symmetry, the product o. the parities o. the initial and
Lnal states must also 3e u so that the transition dipole moment integral (Appendi $+ as a
6hole is g7 By 3oth arguments the parity selection rule is .ound to 3eP u g and g u
transitions allo6ed, u u and g g .or3idden7 This is 4no6n as the Laporte rule7
)1%% THE :EEMAN E66ECT
Apart .rom interacting 6ith each other, the magnetic Lelds due to the spin and or3ital
motion o. an electron can also interact 6ith an eternally applied magnetic Leld7 The
e..ect o. the interaction is to li.t degeneracy and split spectral lines, as 6as Lrst o3ser/ed
3y !ieter Neeman (#%?5 I #$*,+ in #%$?7 The 0uantum num3ers 6hich determine
the angular momenta o. the electron, l, m
l
, s and m
s
determine the associated
magnetic moments according to the .ollo6ing relationships7 A. 6e choose, as 6e
in/aria3ly do, the B2ais as that along 6hich the angular momentum is 0uantised, the
or3ital motion o. an electron gi/es rise to a magnetic moment in the B2direction7 The
relationship 3et6een the 0uantum num3er .or the B2component o. the or3ital angular
momentum (m
l
+ and the magnetic moment (T
B
+ is deri/ed .rom the classical e0uations
.or the magnetic Leld due
to a circulating electron o. charge

e and mass m
e
in Section #2727*P it is1
T
l
eh`
m
T m
6here T
eh`
=
B
=
2m
e
2m
e
T
B
is the Bohr magneton and the negati/e sign sho6s that the magnetic moment is
antiparallel to the or3ital angular momentum7
T
S
Such a simple analysis is not possi3le .or the magnetic moment due to the spin angular
momentum7 But using the relati/istic <irac e0uation it is .ound that1
B
= g
e
T
B
m
S
= 2.002,T
B
m
S
2 T
B
m
S
g
e
is 4no6n as the electron g2.actor and the approimation, g
e
= 2, is 0uite ade0uate .or
all 3ut the most eacting eperiments or calculations7
A. 6e no6 impose an eternal magnetic Leld 3B4 upon the electron there 6ill 3e an
energy change ( E+ gi/en (Bo #272+ 3y1
E
=
!T
l
+
T
S
"

/
=
!m
l
+
2m
S
"T
B
/
B

gT
B
/
B
(57##7#+
B B
6here /
B
is the component o. the Leld in the B2direction7 An this epression a use.ul eper2
imental parameter, g, has 3een introduced7 The g2/alue deduced .rom the eperimentally
o3ser/ed splitting o. spectral lines pro/ides an immediate num3er .or comparison 6ith
theoretical estimates o. m
l
+
2m
s
7 Where the true atomic electronic states are comple
mitures o. the simple microstates as, due to e..ects li4e spin2or3it coupling they normally
are, the /alue o. g 6ill not 3e the simple integer or hal.2integer 6hich '0uation (57##7#+
might lead us to epect7 Since T
B
= $.2-, #0

2*
J T

#
the energy change, or Neeman
splitting, is /ery small7 Con/erting to 6a/e num3ers, 6e Lnd that T
B
= 0.*?- cm

#
T

#
so that a Leld o. the order o. t6o Tesla is re0uired to produce a splitting o. # cm

#
7 This
eplains 6hy Daraday searched, 6ithout success, .or the e..ect o. a magnetic Leld upon
spectral lines some ,0 years 3e.ore Neeman .ound it7
)1%%1% T$e normal :eeman e""e#t
An #%$? 6hen Neeman Lrst o3ser/ed his eponymous e..ect there 6as no concept o.
electron spin7 But or3ital angular momentum and the associated magnetic e..ects 6ere
readily understanda3le 6ith classical electrodynamics and early studies o. the Neeman
e..ect there.ore ga/e a mied picture7 Some results 6ere easy to interpret and these cases
3ecame 4no6n as eamples o. the normal Neeman e..ect7 The remaining results 6ere
only understood 6hen electron spin and its magnetic e..ects 6ere postulated 3y Goudsmit
and =hlen3ec4 in #$25P prior to that they 6ere said to 3e eamples o. the anomalo1s
Neeman e..ect7 There is also an important relationship 3et6een the Neeman e..ect and the
polarisation o. light 6hich is 3est eplained diagrammatically (Digure 57-+7 The properties
o. polarised light are discussed in detail in Section %72 and that discussion 6ill not 3e pre2
empted here7 An discussing Digure 57- 6e shall simply ma4e a num3er o. 3ald statements
6hich 6ill 3e elucidated in Chapter %7
A
#
S
0
to
#
!
#
transition in the a3sence o. a magnetic Leld is illustrated in Digure
57-(a+7 An eample 6ould 3e the Fe?s
2
to Fe?s
#
?p
#
transition o. 3arium 6hich is .ound
at < = 55,.-0 nm and is responsi3le .or the 3right green colour o. the Oame test .or
3arium7 The spectrum appears as a single line since, although there are three upper states
(5
Q
= +
# 0

#+, they are all o. e0ual energy7 An Digure 57-(3+ our atom sample has
3een placed at the centre o. a solenoid so that it is su3@ect to a magnetic Leld (/ +, 6hich
is parallel to the light 3eam7 The magnetic Leld li.ts the degeneracy o. the
#
!
#
state
as re0uired 3y '0uation (57##7#+ so that it is no6 possi3le, in principle, to o3ser/e three
transitions .rom the ground to the ecited state7 Durthermore, the upper state energy le/els
ha/e angular momentum characterised 3y the 0uantum num3ers Q = # and 5
Q
= 0 #7
; S
; S
hn
;
hn
S
hn
; S
#
!
#
#
S
0
B = 0 B HH to light
B to light
+1
0
1
rcp lcp
s p s
(a+ (3+ (c+
6ig;re )1+ The normal Neeman e..ect in the
#
S
0
to
#
!
#
transition o. 3arium
There.ore, in order to conser/e angular momentum, the photon must pro/ide the angular
momentum re0uired .or transitions .rom ground state to the 5
Q
le/els o. the ecited state,
since the lo6er state has no angular momentum7 Circularly polarised light has eactly
the properties 6e re0uireP an angular momentum o. # and .or right circularly polarised
(rcp+ photons a B2component o. # and .or lcp photons +#7 Thus, i. 6e use circularly
polarised light in the Neeman eperiment 6e shall 3e a3le to see the transitions to the

# states 3ut the transition to 5


Q
=
0 6ill not 3e o3ser/ed since the B2component o. the
angular momentum cannot 3e conser/ed7
But i. 6e 3ore a hole in our solenoid and illuminate the atom sample 6ith a light 3eam
perpendicular to the direction o. the magnetic Leld (Digure 57-(c++, a ne6 polarisation
possi3ility emerges7 The oscillating electric and magnetic Lelds, 6hich are the .undamental
carriers o. the polarisation property, can only oscillate in the plane perpendicular to the
direction o. propagation o. the light7 With the eperimental arrangement o. Digure 57-(c+
the light can 3e polarised in the direction o. the Leld and i. 6e use plane polarised light
transitions to all three ecited sates can 3e seen7 The transition to 5
Q
=
0 is energised 3y
light polarised parallel to / and is denoted 3y ( (Gree4 p .or parallel+7 The transitions to
5
Q
= # are energised 3y light polarised perpendicular to / and are denoted 3y ' (Gree4 s
.or German sen4recht = perpendicular+7 The total pro3a3ility o. the transitions in each
o. the three Lgures is the same7 A. 6e set it to .our ar3itrary units in Digure 57-(a+, then
6e ha/e t6o .or each o. the transitions in Digure 57-(3+ and one .or each ' and 2 .or ( in
Digure 57-(c+7 8ery important practical use o. the Neeman e..ect is made in 0uantitati/e
analytical atomic spectroscopy 6here the a3ility to mo/e an a3sorption line 3y applying a
2
magnetic Leld ena3les the 3ac4ground o. the line to 3e measured and su3tracted7 Dinally,
6e note that the eperimentally o3ser/ed separation 3et6een the outer lines gi/es a /alue
o. g o. #702 6hich is 2 Y larger than the theoretical /alue o. #707 This pro3a3ly arises
3ecause o. miing, 3rought a3out 3y spin2or3it coupling, 6ith states ha/ing S = 0, 6hich
3rings us to the anomalous Neeman e..ect7
)1%%1& T$e anomalo;s :eeman e""e#t
When Goudsmit and =hlen3ec4 proposed that electrons had an intrinsic spin angular
momentum characterised 3y the angular momentum 0uantum num3er o.
#
3ut 6ith a
g2/alue o. 270, t6ice as large as the g2/alue .or or3ital angular momentum, the puKKling
splitting patterns o3ser/ed in many spectra 6ere rapidly elucidated and a .ormula epress2
ing the g2/alue in terms o. the 0uantum num3ers L S and Q 6as deri/ed 3y Al.red Lande
b (#%%% I #$-5+, see Section #2721
Q !Q + #" + S!S + #" L!L + #"
g = # +
2Q !Q
!5.##.2"
+ #"
This .ormula gi/es the g2/alues o. 07500, #7#?- and #7,,, .or
,
<
#
,
,
<
2
and
,
<
,
respec2 ti/ely7 These Lgures may 3e compared 6ith the eperimental data .or
corresponding states o. calcium 6hich are 0750#, #7#?2 and #7,2$7 The sodium <2lines
pro/ide a good illus2
tration o. the anomalous Neeman e..ect (Digure 57%+7 The /alues o. 5
Q

g in Digure 57%
are simply the product o. the 5
Q
/alue o. the state and the its g2/alue as determined 3y
'0uation (57##72+ and they are directly related to the spacing o. the spectral linesP e7g7
.or
2
P
,
S =
#
L = # Q =
,
gi/ing g =
*
6hence 5
Q
g = 2 and
2
7
2 2 , ,
2
2
!
#H2
2
S
#H2
C
J
_g
+1/3
1/3
+1
1
2
!
,H2
2
S
#H2
C
J
_g
+6/3
+2/3
2/3
6/3
+1
1
(a+
(3+
6ig;re )1, The anomalous Neeman e..ect on the sodium < lines
Boes .or Chapter 5 #2#
0
)1%& 8I85I2RA!HY AN3 6URTHER REA3IN
#7 L7 !auling and '7B7 Wilson, :ntrod1ction to 31ant1m 5echanics, CcGra629ill, ;e6 Ror4,
#$,5, and <o/er7
27 97 'yring, J7 Walter and G7'7 >im3all, 31ant1m Chemistry, Wiley, ;e6 Ror4, #$**7
,7 Shapes and polar plots o. .2or3itals7 97G7 Driedman, Jr7, G7:7 Choppin and <7G7 Deuer3acher,
Q. Chem. Ed1cation, (%, ,5* I ,5%, #$?*7 C7 Bec4er, Q. Chem. Ed1cation, (%, ,5% I ,?0,
#$?*7
*7 '7=7 Condon and G797 Shortley, -he -heory of Atomic S%ectra, Cam3ridge =ni/ersity !ress,
#$,57
57 :7<7 Co6an, -he -heory of Atomic Str1ct1re and S%ectra, Cali.ornia =ni/ersity !ress, Ber4eley,
#$%#7
?7 J7C7 Slater, 31ant1m -heory of Atomic Str1ct1re, 8ols7 A and AA, CcGra629ill, ;e6 Ror4, #$?07
-7 :7A7 Beth, Phys. Rev., (,, *-# (#$,5+P )., ##5 (#$,?+7
82D )1% T$e spe#tral series o" t$e $0/rogen atom
An #%$0 Johannes :o3ert :yd3erg (#%5* I #$#$+ 6rote the Balmer .ormula .or the
lines in the emission spectrum o. the hydrogen atom in the .orm 6hich is most
common today1

# #

> = R
r
2

s
2
9ere, > is the /alue in 6a/e num3ers (cm

#
+ o. the spectral line, R the
:yd3erg constant (#0$ ?--75-% cm

#
+ and r and s the principal 0uantum num3ers o.
the lo6er
and upper states connected 3y the transition respecti/ely7 =sing this .ormula the L/e
3est24no6n series o. hydrogen lines may 3e characterised as in the .ollo6ing ta3le7
Series r s Lrst line last line
>
(cm

#
+
<
(nm+
>
(cm

#
+
<
(nm+
Lyman (#$0?+ # 2, ,, . . . %2 25%72 #2#7? #0$ ?--7? $#72
Balmer (#%%5+ 2 ,, *, . . . #5 2,27$ ?5?75 2- *#$7* ,?*7-
!aschen (#$0%+ , *, 5, . . . 5 ,,#7? # %-57? #2 #%?7* %207#
Brac4ett (#$22+ * 5, ?, . . . 2 *?-7% * 05272 ? %5*7$ # *5%7%
!.und (#$2*+ 5 ?, -, . . . # ,*075 - *5$7$ * ,%-7# 2 2-$7*
The last line in each series corresponds to a transition in 6hich the upper state has
the principal 0uantum num3er o. inLnity in each case (Digure B57#7#+7 An this state the
electron has the highest energy it can ha/e and still 3e 3ound to the nucleus7 At higher
energies the electron lea/es the atom, i7e7 ionisation ta4es place7 There.ore, all series
ha/e a common upper le/el .or their transition o. highest energyP the ionisation limit7
But the energy re0uired to reach it diminishes since each series starts .rom a higher
le/el7 SchroM dingerGs result .or the eigen/alues o. the hydrogen atom ('0uation
(57#7#++
sho6s that, in cm

#
1
me
*
R
=
%ch
,
?
2
'lectron 3inding energy (#0
,
cm
#
+
#20 #00 %0 ?0 *0 20 0
l = #2#7? nm
l = #027? nm
?5?75 nm
l = $-7, nm
*%?7# nm
l = $570 nm
*,*70 nm
l = $,7% nm
*#072 nm
AoniKation
l = $#72 nm
,?*7- nm
# 2 , * n
Lyman
6ig;re 8)1%1% The Lyman and Balmer series o. the hydrogen atom
Balmer
82D )1& Inter9ele#troni# rep;lsion< spin9or?it #o;pling FS2CG an/ t$eir e""e#t
;pon transition pro?a?ilit0 an/ sele#tion r;les
The purpose o. this Bo is to pro/ide a .airly detailed eample o. the 6ay in 6hich
the relati/e magnitudes o. inter2electronic repulsion and S"C a..ects not only state
energies, as illustrated in Digure 57?, 3ut also 6a/e.unctions and hence transition
pro3a3ilities7 This 6ill also o..er an opportunity to illustrate ho6 transition pro3a2
3ilities are calculated .rom atomic 6a/e.unctions7 The eample 6ill 3e 3ased on the
conLguration p
2
and a transition to that conLguration .rom s
#
p
#
7 We 3egin 6ith
a discussion o. p
2
7
T$e energies o" t$e p
&
#onBg;ration
We ha/e .ound the terms o. p
2
in the LS and && limits in Section 57$, 3ut the methods
used there do not re/eal the com3inations o. microstates, i7e7 the 6a/e.unctions, 6hich
are associated 6ith each term7 These can 3e o3tained .or the limiting cases 3y use o.
the raising and lo6ering operators in the 6ay illustrated .or d
2
in Appendi #0, 3ut .or
the intermediate case 6hich concerns us here 6e re0uire to diagonalise (Appendi ,+
simultaneously the matrices o. the operators .or S"C, V l

s, and inter2electronic
repul2
sion, e
2
,r
#2
7
The 3asis states or microstates may 3e 6ritten in the .orm (m
l#
m
s#
m
l2
m
s2
+
6ith the m
s
/alues represented 3y a superscript plus or minus sign, e7g7 (+#
+

0

+, it
3eing al6ays understood that the microstate is actually a Slater determinant (Appendi
?+, i7e71

!
+
#
+
0

"
=
!#, 2"{|+#
+
!#"0

!2" |0

!#" + #
+
!2" }
ZA. the t6o electrons are not 3oth p2electrons it 6ould usually 3e necessary to
include the 0uantum num3er l in the notation7\ Dor p
2
there are #5 microstates and in
the matrices 6hich .ollo6 6e shall consider #0 o. them, those ha/ing 5
Q
/alues o.
+
2,
+
# and 07 The matri elements .or 5
Q
=
2 and

# are, o. course, /ery similar


to those .or 5
Q
= +
2 and
+
#7 We shall not go into the details o. the calculation o.
the electron2repulsion matri elements7 Dull treatments o. this su3@ect can 3e .ound in
numerous sources7
#I,
The re0uired integrals can 3e epressed as a sum o. products o.
angular and radial parts the Lrst o. 6hich can 3e o3tained in closed .orm and ta3ulated
.or any com3ination o. spherical harmonics (Appendi 5+, i7e7 .or all atoms7 The radial
integration, on the other hand, depends upon the radial .unctions 6hich di..er .rom
atom to atom and they must 3e determined indi/idually, either theoretically or 3y
comparison 6ith eperiment, .or each atom7 9o6e/er, the results can 3e epressed
in terms o. a small num3er o. integrals, D
0
and D
2
in the present case, 6here1


D
;
!n
a
l
a
n
*
l
*
"
=
e
2
!r
;
,r
;+#
":
#
2
!n
a
l
a
":
2
2
!n
*
l
*
"r
2
r
2
dr
#
dr
2 P R # 2
0 0
:(nl + is the radial part o. an atomic 6a/e.unction .unction, r
P
is the smaller and r
R
the larger o. r
#
and r
2
, and the electron repulsion is o3tained as a sum o. t6o terms,
A
0
D
0
+ A
2
D
2
, 6here A
0
and A
2
are the results o. the angular integrations7
The inter2electronic repulsion matri .or the microstates o. p
2
ha/ing 5
Q
= +2
and +# is1
(+#
+
+#

+
(+#
+
+#

+
D
0
+ D
2
,25
(+#
+
0
+
+
0
(+#

0
+
+
0
(+#
+
0

+
0
(+#
+
#
+
+
0
(
+
#
+
0
+
+ 0 D
0

D
2
,5 0 0 0
(
+
#

0
+
+ 0 0 D
0

2D
2
,25

,D
2
,25 0
(
+
#
+
0

+ 0 0

,D
2
,25 D
0

2D
2
,25 0
(
+
#
+

#
+
+ 0 0 0 0 D
0

D
2
,5
The eigen/alues o. this part o. the matri are D
0
D
2
,5 (,+ and D
0
+ D
2
,25
(2+7
The inter2electronic repulsion matri .or the microstates o. p
2
ha/ing 5
Q
=
0 is1
(+#
+
#

+
(+#
+
#

+
D
0
+ D
2
,25
(+#

+
0
(+#

#
+
+
?D
2
,25
(0
+
0

+
+,D
2
,25
(#
+
0
+
+
0
(
+
#

+ 0 D
0

D
2
,5 0 0 0
(
+
#

#
+
+

?D
2
,25 0 D
0
+
D
2
,25

,D
2
,25 0
(0
+
0

+
+
,D
2
,25 0

,D
2
,25 D
0
+
*D
2
,25 0
(

#
+
0
+
+ 0 0 0 0 D
0

D
2
,5
The eigen/alues o. this part o. the matri are D
0
D
2
,5 !,", D
0
+ D
2
,25 !#"
and D
0
+
2D
2
,5 !#

"7
#

#

0 #

0 #

# #
i
2
#
2
The remaining L/e states o. the electron2repulsion matri gi/e eigen/alues o.
D
0
+ D
2
,25 !2" and D
0
D
2
,5 !," so that in total 6e ha/e1 D
0
D
2
,5 !$", D
0
+
D
2
,25 !5" and D
0
+ 2D
2
,5 !#"7 Since D
0
appears on each diagonal element and
no6here else it simply sets the a3solute energy scale and can usually 3e set to Kero7
Thus, these are the states
,
!,
#
< and
#
S 6hich, 6ith D
0
= 0 and D
2
= 25 ar3itrary
units, correspond in energy and degeneracy to the etreme le.t o. Digure 57?7 The
corresponding 6a/e.unctions can 3e o3tained as com3inations o. microstates 3y diag2
onalising the 3loc4ed out matrices7 The energy matri .or p
2
in the a3sence o. S"C
is seen to 3e a .unction only o. D
2
6hich can 3e treated as a parameter and its /alue
o3tained 3y comparison o. calculated and eperimental energy le/els7
The matri elements o. the S"C are more readily o3tained than those o. electron
repulsion7 We epress the operator in the .orm o. a sum o/er (in this case t6o+
electrons1
V

l

i
s
i
= V

#
2
!l

i
+s

i

+
l

i
s

i
+"
+
l

iB
s

iB
i i
At is use.ul to dra6 up the .ollo6ing ta3le1
|+#
+
|0
+
|#
+
|+#

|0

|#

+
s

0

2|+#

2|0
+
0 0 0 l

s
+
0 0
0

2|0
+

2|#
+
0
l

B
s

B
#
|+
#
+

0

#
|
#
+

#
|+
#


0
#
|
#

2 2 2 2
l


s

#
+
#

#

#
+
#
+
#

#
+
#

|+ |+ | | | |+ | |
2 2 2 2 2 2 2 2
Drom 6hich, .or eample1
V

l

i
s
i
|+#
+
0
+
= V
#
2
|+
#
+
0
+
+
V

|+#
+
+ #


gi/ing rise to an on2diagonal matri element o.
#
V and an o..2diagonal element o.

#
2
2
2
V 6ith
+
#
+
+
#

|
7 The S"C matri .or the microstates o. p
and +# is1
ha/ing 5
Q
= +
2
(+#
+
+#

+ (+#
+
0
+
+ (+#

0
+
+ (+#
+
0

+ (+#
+
#
+
+ (+#
+

+#

+ 0 V ,

2 0 0 0 (
+
#
+
0
+
+ V ,

2 V ,2 0 0 0
(+#

0
+
+ 0 0 V ,2 0 0
(+#
+
0

+ 0 0 0 V ,2 V ,

2
(+#
+
#
+
+ 0 0 0 V ,

2 0
The eigen/alues o. this part o. the matri are +V !2" and
#
V !,"7
2
2
The S"C matri .or the microstates o. p
2
ha/ing 5
Q
= 0 is1
(
+
#
+

+ (
+
#

+ (
+
#

#
+
+ (0
+
0

+ (

#
+
0
+
+
(+#
+
#

+ V 0 0 0 0
(+#

+ 0 V ,2 V ,

2 V ,

2 0
(0
+
0

+ 0 V ,

2 0 0 V ,

2
(#
+
0
+
+ 0 0 V ,

2 V ,

2 V ,2
The eigen/alues o. this part o. the matri are +V !2 ",
#
V !2 " and 2V !# "7
When the results .or 5
Q
= # and 2 are included the #5 eigen/alues o. the spin2
or3it matri are .ound to 3e 2V !# ",
#
V !% " and +V !? " 6hich corresponds
to the etreme right o. Digure 57? 6ith V = 5 ar3itrary units7
Anspection o. the matrices o. V l


s

and e
2
,r
#2
sho6s that they are 3loc4ed out,
though not in eactly the same 6ay .or 3oth operators7 The inter2electronic repulsion
connects, i7e7 has an o..2diagonal matri element 3et6een, microstates 6hich ha/e the
same /alue o. 5
L
and the same /alue o. 5
S
6hereas the S"C lin4s microstates 6ith
the same /alue o. 5
Q
!
=
5
L
+
5
S
"7 9o6e/er, not all pairs o. states 6hich satis.y
these re0uirements are connected 3y an operator7
An cases o. intermediate coupling, 6here the S"C and inter2electronic repulsion
are o. compara3le magnitudes, 6e must sum the t6o matrices and diagonalise the
result7
A similar analysis o. the energetics o. the s
#
p
#
conLguration might 3e made, 3ut
this is not necessary .or our present purposes and it su.Lces to say that the .ollo6ing
terms are possi3leP
#
! and
,
! in the a3sence o. S"C and
#
!
#
,
,
!
2
,
,
!
#
and
,
!
0
6hen it is present7
Atomi# transition pro?a?ilities
Dirst, some preliminary o3ser/ations7 Apart .rom the Bohr2'instein condition, the
selection rules o. atomic spectroscopy are couched in terms o. the 0uantum num3ers
6hich descri3e particular aspects o. the angular momentum o. the atom7 We shall
assume that the Bohr2'instein condition is satisLed and concentrate on the condi2
tions on the 0uantum num3ers7 8ery general deri/ations o. the selection rules 6hich
rely on ad/anced angular momentum theory can 3e .ound in the specialist tets on
atomic spectroscopy7
#I,
9ere 6e shall conLne our attention to speciLc eamples
6hich illustrate the general results7
The intensity o. an electronic transition .rom an initial or3ital, $
i
, to a Lnal or3ital,
$
.
, in a one2electron atom is proportional to the s0uare modulus o. the transition
moment integral (Appendi $ and Section %7-+, i7e7 : | $
.
|er|$
i
|
2
6here e is the
electronic charge and r the /ector distance 3et6een the electron and the nucleus7 Dor
a many2electron atom : | G
.
|
;
er
;
|G
i
|
2
6here the sum o/er ; runs o/er all the
electrons and G
.
and G
i
represent electronic states7 The transition moment operator
is a one+electron operator 6hich means that .or a non2Kero TC integral the states
,

represented 3y G
i
and G
.
can only di..er 3y one or3ital 3ecause, .or eample, o. the
n terms in the .ollo6ing sum1
G
.
|
4
er
;
|G
i
= $
a
!#"$
*
!2"$
c
!," . . . $
n
!n"|
;
er
;
|$
a
!#"$
*
!2"$
x
!," . . . $
n
!n"
only1
$
c
!,"|er
,
|$
x
!," $
a
!#"|$
a
!2" $
*
!2"|$
*
!2" . . . $
n
!n"|$
n
!n"
may ha/e a /alue, all the others 3eing Kero 3ecause o. the orthogonality o. the atomic
or3itals $
c
and $
x
7
T6o approaches are open to us 6hen 6e see4 to e/aluate a TC integral such as

$
c
!,"
|
er
,
|
$
x
!,"

, one emphasises angular momentum and the other geometrical .ac2
tors7 Atomic or3itals can 3e .ormulated in a manner such that they are eigen.unctions
o. the angular momentum operators l

and l

B
7 An order to eploit this property 6e
6rite the operator er in a .orm appropriate .or le.t2 or right2circularly polarised light
(Section %7?+, using the common notation m

and m
+
respecti/ely1

lcp

m

=
!e, 2"!x iy" = !e

2"!r sin # cos $ ir sin # sin $"


= !er sin #,

2" ep!i$"

rcp

m
+
=
!e, 2"!x + iy" = !e,

2"!r sin # cos $ + ir sin # sin $"


= !er sin #,
2" ep!+i$"
Since the radial part o. an atomic or3ital is di..erent .or e/ery or3ital and e/ery
atom, only angular integration is appropriate at this point7 :adial integration can
only 3e carried out 6hen the radial .unctions o. the or3itals concerned are speciLed7
We Lnd that the only non2Kero matri elements 3et6een s and p or3itals in this
.ormulation are1

p
|
m

|
s
=
er,
, and p +

|
m
+
|
s
=
er, ,
This .orm o. TC integral is use.ul 6hen 6e 6ish to interpret spectra measured in
magnetic Lelds, as in the Neeman e..ect and magnetic circular dichroism, 6here the
le/els are split according to their m
l
/alues (Section 57## and Digures 57- and 57%+7
A. 6e epress the p2or3itals as p
x
, p
y
and p
B
and 6rite er as1
m
x
= er sin # cos $ m
y
= er sin # sin $ and m
B
= er cos #
6e Lnd that the only non2Kero TC integrals are1


p
x
|
m
x
|
s
=
p
y
|
m
y
|
s
=
p
B
|
m
B
|
s
=
er, ,
This .ormulation is appropriate .or spectra in 6hich the atom is in a non2spherical
en/ironment, e7g7 6hen su3@ected to an electric Leld7
We can no6 return to the 0uestion o. transitions 3et6een states o. the conLgura2
tions s
#
p
#
and p
2
7 Since the microstates (+#
+
+#

+ and (+#
+
0
+
+ appear at the top
and to the le.t o. Ta3le 57*, they must .orm components o. the states
#
E and
,
P o. p
2
respecti/ely7 Also, the matri o. inter2electronic repulsion sho6s that in the a3sence
o. S"C there is no miing 3et6een these states, nor do they interact 6ith any others7
2
Thus 6hen V = 0, the .ollo6ing 6a/e .unctions are true descriptions o. components
o. the
#
< and
,
! states o. p
2
1
#
< !p
2
" = !#,

2"{|+#
+
!#" + #

!2" |+#

!#" + #
+
!2" }
,
! !p
2
" = !#,

2"{|+#
+
!#"0
+
!2" |0
+
!#" + #
+
!2" }
;ote that the a3o/e 6a/e .unctions are o3tained 3y the epansion o. the Slater
determinants (Appendi ?+ represented 3y the microstates (+#
+
+#

+ and (+#
+
0
+
+7
Similar considerations sho6 that .or the conLguration s
#
p
#
6e can 6rite1
#
! !s
#
p
#
" = !#,2"{|s
+
!#" + #

!2" |+#

!#"s
+
!2"
|s

!#" + #
+
!2" + |+#
+
!#"s

!2" }
,
! !s
#
p
#
" = !#,2"{|s
+
!#" + #

!2" |+#

!#"s
+
!2"
+ |s

!#" + #
+
!2" |+#
+
!#"s

!2" }
We no6 calculate some transition moment integrals 3et6een the a3o/e states, using
the notation M = m
#
+ m
2
= er
#
+ er
2
7
# 2 # # # #

+ +

<!% "
|
M
|
P !s % "
=
!
2
2"{ +# !#" + # !2"| +# !#" + # !2"||M|
|s
+
!#" + #

!2" |+#

!#"s
+
!2" |s

!#" + #
+
!2" + |+#
+
!#"s

!2" }
= !
#

2"{ +#
+
!#" + #

!2"|M|s
+
!#" + #

!2"
+ +#
+
!#" + #

!2"|M|+#
+
!#"s

!2" + +#

!#" + #
+
!2"|M| + #

!#"s
+
!2"
+ +#

!#" + #
+
!2"|M|s

!#" + #
+
!2" }
The a3o/e reduction .rom eight integrals to .our is possi3le 3ecause those terms
in 6hich the m
s
/alue o. the electron is di..erent on either side o. the operator, e7g7
+
#
+
!#"
+
#

!2"
|
M
|+
#

!#"s
+
!2"

, are Kero 3ecause o. the integration o/er the spin
co2ordinates7 As an eample o. a non2Kero contri3ution to the transition moment 6e
can e/aluate1
+#
+
!#" + #

!2"|M|s
+
!#"+#

!2" = +#
+
!#" + #

!2"|m
#
+ m
2
|s
+
!#" + #

!2"
= +#
+
!#" + #

!2"|m
#
|s
+
!#" + #

!2" + +#
+
!#" + #

!2"|m
2
|s
+
!#" + #

!2"
= +#
+
!#"|m
#
|s
+
!#" +#

!2"|+#

!2" + +#
+
!#"|s
+
!#" +#

!2"|m
2
|+#

!2"
= +#
+
!#"|m
#
|s
+
!#"
3ecause o. the orthonormality o. the atomic or3ital 6a/e .unctions7 All .our integrals
# 2 # # #


gi/e the same contri3ution so that E!% "|M| P !s % " = 2 +#
|m|s
7 ;ote
that this is a transition in 6hich S
=
0, L
=
0 and 5
L
= +
#P although 6e ha/e
a t6o2electron atom 6e Lnd that the selection rules .or one2electron atoms apply
3ecause electron repulsion does not mi states 6ith di..erent S, L or 5
L
/alues7
ZThe reader may 6ish to conLrm, simply 3y changing a .e6 signs in the a3o/e
e0uations, that1
# 2 , # #
<!% "|M| P !s % " = 0 as epected since S = #\
But, as the a3o/e S"C matri sho6s, S"C mies states 6hich ha/e di..erent S, L
or 5
L
/alues7 We can illustrate the e..ect o. this 3y considering the t6o states in the
top le.t2hand corner o. the electron2repulsion and S"C matrices 6hich no6 interact
6ith each other 3ut 6ith no other states7 Adding the t6o matrices 6e ha/e the matri
on the le.t1
(+#
+
+#

+ (+#
+
0
+
+ (+#
+
+#

+ (+#
+
0
+
+ (+#
+

+#

+ D
0
+ D
2
,25 V ,

2 === 0 V ,

2 (+#
+
0
+
+
V ,

2 D
0
D
2
,5 + V ,2 V ,

2 V ,2 *D
2
,5
Since only the di..erence 3et6een the t6o diagonal matri elements is important here,
6e may su3tract D
0
+ D
2
,25 .rom each diagonal element and o3tain the right2hand
matri a3o/e7
A. 6e no6 suppose that V ,2
=
*D
2
,5, 6hich corresponds closely to the position
o. lead in Digure 57?, the diagonal elements are e0ual and there is an e0ual miing
o. (+#
+
+#

+ and (+#
+
0
+
+7 We can no6 no longer spea4 o. pure
#
E!%
2
" and ,
P !%
2
" statesP the eigenstates o. the atom are e0ual mitures o. the t6o7 There.ore,
transitions .rom
#
P !s
#
%
#
" to the states Lrst descri3ed as
#
E!%
2
" or
,
P !%
2
" 6ill
3e e0ually allo6ed 3ecause o. their component o.
#
E!%
2
"7 We see that the
apparent .ailure o. the selection rules is 3etter descri3ed as a .ailure in the correct
designation o. the states in/ol/ed7 The selection rules on one2electron matri elements
are al6ays rigorously o3eyed, in the a3sence o. pertur3ations, and the pro3lem lies
6ith our 4no6ledge o. the eact 6a/e.unctions o. the states in/ol/ed in the
transition7 At
should also 3e pointed out that the large S"C 6ill also cause the
#
P !s
#
%
#
" state
to
mi 6ith the
,
P !s
#
%
#
" 6hich may .urther complicate matters7 ". course, it
might 3e argued that in this case o. a high degree o. miing the situation 6ould 3e
clearP 3ut i. 6e mo/e across Digure 57? to the position o. tin, .or eample, 6e
Lnd that
D
2
=
2.%*- e8, V
=
0.2?0 e8 and H
=
5V ,D
2
=
0.*?7 The energy matri is then1
(+#
+
+#

+ (+#
+
0
+
+
(
+
#
+

+
#

+ 0 072?0
(
+
#
+
0
+
+ 072?0
27#*%
.or 6hich the mied 6a/e .unctions
#
E

!%
2
" or
,
P

!%
2
" are1
#
<

!%
2
" = 0.$$,
#
E!%
2
" + 0.##$
,
P !%
2
"
and
,
P

!%
2
" = 0.##$
#
E!%
2
" 0.$$,
,
P !%
2
"
Dor the tin atom, there.ore, it seems 0uite reasona3le to descri3e the states as
#
E!%
2
" and
,
P !%
2
", though 6e ha/e to recognise that the selection rules 6ill not
3e strictly o3eyed 3ecause o. the miing induced 3y S"C7 Dor germanium, .or
6hich
D
2
=
,.#52 e8, V
=
0.#0$ e8 and H
=
0.#- the miing is negligi3le and the limiting
LS selection rules should hold7
!ro3lems .or Chapter 5 #2$
At is 6orth noting that, although it is the S"C 6hich causes the miing o. states
o. di..erent multiplicity, the degree o. miing depends upon the energy2separation
3et6een the miing states and there.ore upon the inter2electronic repulsion7 An ger2
manium, though the miing o. states is /ery small, the S"C ma4es a measura3le
impact on the state energies through the diagonal matri element 6ith (
+
#
+
0
+
+7
Where only diagonal elements o. S"C are signiLcant in the comparison o. theory
and eperiment 6e spea4 o. Crst+order S"C7
RE6ERENCES
#7 '7=7 Condon and G797 Shortley, -he -heory of Atomic S%ectra, Cam3ridge =ni/ersity !ress,
#$,57
27 J7C7 Slater, 31ant1m -heory of Atomic Str1ct1re, 8ols7 A and AA, CcGra629ill, ;e6 Ror4,
#$?07
,7 :7<7 Co6an, -he -heory of Atomic Str1ct1re and S%ectra, Cali.ornia =ni/ersity !ress,
Ber4eley, #$%#7
!R285EMS 62R CHA!TER )
#7 !redict the .re0uencies and 6a/elengths o. a .urther series in the electronic spectrum
o. the hydrogen atom7
27 Calculate the 6a/elength o. the Lrst QBalmerG line in the spectra o. the deuterium atom
and the Be
,
+
cation7
,7 Sho6 that the num3er o. states, N
states
, in a conLguration l
%
, 6here l is the or3ital
angular momentum 0uantum num3er and % is the num3er o. electrons, is1
N
states
= 2lU,{%U !2l %"U}
9ence, conLrm the .act that there are #00# states o. f
*
ZnU = n!n #"!n 2" . . . #\
*7 <ra6 up a ta3le analogous to Ta3le 57* .or the conLguration sd and determine the
states o. the system7
57 <ra6 up a ta3le analogous to Ta3le 57? .or the conLguration sd 6ith && coupling and
determine the states o. the system7
?7 The normalised radial 6a/e .unctions .or the hydrogen atom are gi/en in Appendi 57
Sho6, using the .unctions .or n = ,, that although they are di..erent all those ha/ing
the same /alue o. n gi/e the same result .or the integral1


Oe
2
2

R
,l
!r "
*(? r
R
,l
!r "r
O
2
e
2
n
2
dr =
,2*(? a
.
0 0 0 0
This result tells us that the potential energy o. the electron is the same in all three
types o. d or3ital, despite the di..erences in their radial .unctions7 Because o. the /irial
theorem, this means that the 4inetic and total energies 6ill also 3e the same7 <etermine
the 4inetic and total energy o. a hydrogen ,d electron and compare your ans6er 6ith
'0uation (57#7#+7
-7 =se the in.ormation on s p transition pro3a3ilities in Bo 572 to conLrm the relati/e
intensities o. the spectral lines o. 3arium 0uoted in Section 57##7# and illustrated in
Digure 57-7
Chapter ?
T$e CoAalent C$emi#al 8on/
?70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #,2
?7# The 3inding energy o. the hydrogen molecule . . . . . . . . . . . . . . . . . . . . #,,
?72 The 9amiltonian operator .or the hydrogen molecule . . . . . . . . . . . . . . . #,*
?7, The Born I "ppenheimer approimation . . . . . . . . . . . . . . . . . . . . . . . . #,?
?7* 9eitler and London1 The /alence 3ond (8B+ model . . . . . . . . . . . . . . . . #,-
?75 9und and Culli4en1 the molecular or3ital (C"+ model . . . . . . . . . . . . . . #,$
?7? Ampro/ing the 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7?7# The /alue o. N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7?72 !olarisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7- =niLcation1 Aonic structures and conLguration interaction . . . . . . . . . . . . #*#
?7% 'lectron correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*,
?7$ Bonding and anti3onding C"s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*5
?7#0 Why is there no 9eI9e BondJ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*?
?7## Atomic or3ital o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*?
?7##7# ' (sigma+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*-
?7##72 ( (pi+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*-
?7##7, ) (delta+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*%
?7##7* ;on23onding o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*%
?7#2 The homonuclear diatomic molecules .rom lithium to Ouorine . . . . . . . . . #*$
?7#, 9eteronuclear diatomic molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5#
?7#* Charge distri3ution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#5 9y3ridisation and resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#57# 9y3ridisation1 !auling #$,# . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#572 9y3ridisation and the /alence 3ond theory . . . . . . . . . . . . . . . . #5?
?7#57, 9y3ridisation o. car3on A"s . . . . . . . . . . . . . . . . . . . . . . . . . #5?
?7#57* The choice o. hy3rid or3itals . . . . . . . . . . . . . . . . . . . . . . . . . #?#
?7#575 The properties o. hy3rid2or3ital 3onds . . . . . . . . . . . . . . . . . . . #?2
?7#? :esonance and the /alence 3ond theory . . . . . . . . . . . . . . . . . . . . . . . . #?,
?7#- Colecular geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?,
?7#-7# The /alence2shell electron2pair repulsion (8S'!:+ model . . . . . . #?*
?7#-72 The 8S'!: model and multiple 3onds . . . . . . . . . . . . . . . . . . . #?5
?7#% Computational de/elopments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?-
?7#$ Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?%
!ro3lems .or Chapter ? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #-?
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
#,2 The Co/alent Chemical Bond
*1. INTR23UCTI2N
There can 3e no dou3t that the most important contri3ution o. 0uantum mechanics to the
science o. chemistry is the 6ay in 6hich it has ena3led us to understand the nature o. the
chemical 3ond, especially the co/alent 3ond7 The long and comple story o. the theory
o. /alency and the chemical 3ond 3e.ore the ad/ent o. 0uantum mechanics has 3een 6ell
told 3y !almer
#
and 3y :ussell
2
and 6ill not 3e repeated here7 We set the o3@ecti/es o.
this chapter 3y dra6ing .rom the Lrst .e6 pages o. a 3oo4 3y one o. the pioneers in the
application o. 0uantum mechanics to chemistry, Charles Al.red Coulson (#$#0 I #$-*+7
An his 3est2selling undergraduate tet, Q8alenceG,
,
Coulson discussed the ma@or
eperimental phenomena 6hich any /alid theory o. chemical 3onding must eplain7 9e
raised, in particular, the .ollo6ing 0uestions1
Why do molecules .orm at allJ Why is it that t6o hydrogen atoms .orm the /ery sta3le
diatomic molecule 9
2
6hile t6o helium atoms do not .orm 9e
2
J
Why is there saturation o. /alency, i7e7 i. 9
2
is sta3le, 6hy not 9
,
or 9
*
and so onJ
Similarly, 6hy do 6e ha/e C9
*
3ut not C9
5
or C9
?
J
What are the reasons .or the shapes o. moleculesJ Why, .or eample, is the car3on
dioide molecule (C"
2
+ linear 3ut sul.ur dioide (S"
2
+ 3ent, 6ith an " I S I "
3ond
angle o. ##$

J
Durther, the theory must lin4 the interpretations o. the a3o/e eperimental .acts together,
/ie6ing them as aspects o. a comprehensi/e theory o. chemical structure as a 6hole 6hich
(and here A add to CoulsonGs re0uirements+ should em3race not only co/alent compounds
3ut also ionic solids and metals7
An #$#$, Ca Born (#%%2 I #$-0+ and DritK 9a3er (#%?% I #$,*+ independently pu32
lished the energetic cycle, no6 4no6n as the Born I 9a3er cycle, 3y means o. 6hich
the energy o. an ionic lattice can 3e epressed in terms o. the properties o. the
elements .orming the lattice and the coulom3ic .orces 3et6een the ions in/ol/ed7 With
that 6or4 the essential .eatures o. the ionic 3ond 6ere 0uantitati/ely understood, though
it must 3e said that the ecellent agreement o. theory and eperiment is a little .ortuitous
due to the sel.compensating nature o. the ionic model, i7e7 the mutual cancellation o.
errors7
*
But the energetic 3asis o. the co/alent 3ond remained a complete mystery and its
eplanation 6as one o. the Lrst o3@ecti/es o. the ne6 0uantum mechanics7 At is amaKing
to note that, 6ithout the aid o. a computer or e/en an electronic calculator, 9eitler and
London produced a calculation o. the 3inding energy o. the hydrogen molecule in #$2-,
@ust one year a.ter the pu3lication o. SchroM dingerGs 6a/e e0uationU Though the
calculation 6as not 0uantitati/ely /ery accurate, 6ays in 6hich it might 3e impro/ed
6ere o3/ious and it 6as clear that 0uantum mechanics 6as on the right trac4 as .ar as
chemical 3onding 6as concerned7 By #$,,, a calculation o. the 3inding energy o. 9
2
correct to 3etter than
07? Y 6as reportedP a .ormida3le achie/ement 6hen 6e consider the compleity o. the
pro3lem, 6hich 6ill soon 3ecome apparent7 This 6or4 is descri3ed no6, gi/ing a roughly
chronological account o. the signiLcant steps in the application o. 0uantum mechanics
to the chemical 3ond in the hydrogen moleculeP this eempliLes almost all the essential
aspects o. the theory7 What it lac4s, the interpretation o. molecular geometry, i7e7 3ond
angles, is descri3ed in Section ?7#-7
The Binding 'nergy o. the 9ydrogen Colecule #,,
*1% THE 8IN3IN ENERY 26 THE HY3R2EN M25ECU5E
Be.ore em3ar4ing upon a discussion o. the calculation o. the 3ond energy o. 9I9, 6e
should 3e clear @ust 6hat is to 3e calculated and ho6 the result is to 3e compared 6ith
eperiment7 We Lrst recall (Section 57#+ that the Kero o. energy is, 3y deLnition, that state
in 6hich all particles, t6o electrons and t6o protons in this case, are inLnitely separated
and at rest so that they ha/e neither 4inetic nor potential energy7 A. 6e no6 allo6 t6o
hydrogen atoms to .orm at rest, the energy o. each atom lies #,7?05 e8 3elo6 the Kero o.
energy and 6e say that the electronic energy o. the hydrogen atom is #,7?05 e87 The
energy o. t6o 9 atoms is 2 #,.?05 = 2-.2#0 e8 (*,.5$? #0

#$
J+ (Digure ?7#P
note the t6o 3rea4s in the scale+7
A. the t6o hydrogen atoms approach su.Lciently close to each other to .orm a 3ond
then there is a .urther decrease in energy and there 6ill 3e a particular /alue o. the 9I9
internuclear distance .or 6hich the energy is a minimum, i7e7 is the most negati/e7 This
distance is 4no6n as the e0uili3rium internuclear distance, R
e
, and is .ound eperimentally
to 3e -*7# pm7 The corresponding eperimental energy is *7-*- e8 (-.?05?

#0

#$
J+
3elo6 the energy o. the t6o, non2interacting hydrogen atoms7 This is the energy 6hich 6e
shall see4 to calculate 3y determining the di..erence 3et6een the electronic energy o. t6o
independent hydrogen atoms and that o. the hydrogen (9I9+ molecule 6ith a 3ond length
o. R
e
7 The sym3ol .or this energy di..erence is E
e
7 Since 6e 4no6 the electronic energy
o. the hydrogen atom /ery accurately, .rom 3oth eperiment and theory, the pro3lem is
simply that o. calculating the electronic energy o. the molecule7
We emphasise the electronic energy 3ecause the molecule also has other .orms o.
energy that are not o. interest to us in the present contet7 At may, .or eample, 3e mo/ing
29
+
+ 2e
070 e8
2 A
9
= 2-72#0
e8
9 + 9
2-72#0 e8
<
0
= *7*-? e8
<
e
= *7-*- e8
9
2
,#7?%? e8
Kero2point energy = 072-# e8
,#7$5- e8
6ig;re *1% 'nergy le/els .or 29
+
+ 2e 29 and 9
2
#,* The Co/alent Chemical Bond
2 2 2
through space and rotating gi/ing rise to 4inetic energy contri3utions to its energy 6hich
6e do not re0uire in our current calculation7 The molecule 6ill also 3e /i3rating and
6e cannot ignore this Bero+%oint vi*rational energy (see Chapter #0 .or more details+
since it impinges upon the comparison o. theory 6ith eperiment7 'perimentally, the
energy re0uired to dissociate the hydrogen molecule into t6o hydrogen atoms is .ound
to 3e *7*-? e87 This is the energy E
0
P the energy re0uired to dissociate a real hydro2
gen molecule 6hich has Kero2point energy, as opposed to the theoretical /alue o. E
e
6hich is the dissociation energy o. an hydrogen molecule 6hich has no Kero2point energy
(Digure ?7#+7 Thus, the energy 6hich 6e see4 to calculate (E
e
+ is gi/en 3y the e0uation1
E
e
= E
0
+ Kero2point energy !?.#.#"
The Kero2point energy o. 9I9 is 4no6n .rom eperiment to 3e 072-# e8 so that,
eperimentally1
E
e
=
*.*-?
+
0.2-#
=
*.-*- e8 !?.#.2"
An the .ollo6ing 6e shall compare theoretical and eperimental /alues o. E
e
7
*1& THE HAMI5T2NIAN 2!ERAT2R
62R THE HY3R2EN M25ECU5E
Dollo6ing SchroM dingerGs method as in earlier chapters, our Lrst step must 3e to
6rite do6n an epression .or the energy o. the hydrogen molecule in classical terms7
9a/ing done that 6e then apply the rules .or con/erting the classical epressions to the
appropri2 ate operators7 A hydrogen molecule in 6hich the nuclei ha/e 3een la3elled A
and B and the electrons # and 2 is represented in Digure ?727 The .act that 6e ha/e so
la3elled the electrons and nuclei should not 3e ta4en to mean that 6e can actually
distinguish 3et6een t6o electrons or t6o nuclei7 ;othing could 3e .urther .rom the
truthP it is .undamental to 0uantum mechanics that all particles o. the same species are
totally indistinguisha3le7 The la3els are used only to ensure that 6e consider all the
possi3le terms in the 9amil2 tonianP the attraction 3et6een e/ery nucleus and e/ery
electron, .or eample7 With the aid o. Digure ?72 6e can identi.y the .ollo6ing energy
terms, their classical2mechanical epressions and the corresponding operators1
#7 The 4inetic energy o. the nuclei1
!5 V
A
"
2
!5 V
B
"
2
h ! + "
A B
25
+
27 The 4inetic energy o. the electrons1
25

(?727#+
%(
2
5
2
!mv
#
"
2
!mv
2
"
2

h
2
!

2
+
"
# 2
2m
+
2m

(?7272+
%(
2
m
,7 The potential energy due to nucleus2electron attraction1
e
2

# # # #

e
2

# # # #

(?727,+
*( ?
0 r
A#
+
r
B#
+
r
A2
+
r
B2

*( ?
0
r
A#
+
r
B#
+
r
A2
+
r
B2
*7 The potential energy due to internuclear repulsion1
e
2
#
e
2
#
!?.2.*"
*( ?
0

:
AB

*( ?
0

:
AB
The 9amiltonian "perator .or the 9ydrogen Colecule #,5
2
r
#2
#
r
A2
r
B2
r
A#
r
B#
A
:
AB
B
6ig;re *1& The 9amiltonian .or the hydrogen molecule
57 The potential energy due to interelectronic repulsion1
e
2
#
e
2
#
!?.2.5"
*( ?
0

r
#2

*( ?
0

r
#2
An these epressions e is the magnit1de o. the charge on the protons and the electrons,
m and 5 are the masses o. the electron and proton respecti/ely and ?
0
is the /acuum
permitti/ity7 The sym3ol
2
, 6hich is spo4en Qdel s0uaredG, is deLned 3y1
2 2 2
2 2 2 2
D ,D + D ,D y + D ,D K
!?.2.?"
"ur total 9amiltonian operator is there.ore the sum o. ten terms and 6e immediately
recognise that it is unli4ely that a solution o. SchroM dingerGs eigen/alue2
eigen.unction e0uation can 3e .ound, e/en .or this, the most simple o. molecules7
There.ore, i. the theory is to 3e applica3le, some 6ay, or 6ays, o. simpli.ying the pro3lem
must 3e .ound7 Such methods ha/e 3een .ound and the story o. the theory o. the
chemical 3ond since
#$2? is one o. Lnding approimate methods that ena3le us to dra6 out the essence o.
the 0uantum2mechanical description, e/en 6hen 6e are /ery .ar .rom Lnding an eact
solution o. SchroM dingerGs e0uation7 The .act 6e are una3le to sol/e SchroM dingerGs
e0uation
Qhead2onG so to spea4 is 3y no means a disaster as t6o eminent theoretical physicists,
'ugen !7 Wigner and Drederic4 SeitK, recognised in #$557 Their opening lines in a re/ie6
5
o. the theory o. the cohesion (3onding+ in metals read as .ollo6s1
QA. one had a great calculating machine, one might apply it to the pro3lem o. sol/ing the SchroM
dinger e0uation .or each metal and o3tain there3y the interesting physical 0uantities, such as the
cohesi/e energy, the lattice constant and similar parameters7 At is not clear, ho6e/er, that a great
deal 6ould 3e gained 3y this7 !resuma3ly the results 6ould agree 6ith the eperimentally determined
0uantities and nothing /astly ne6 6ould 3e learned .rom the calculation7 At 6ould 3e pre.era3le
instead to ha/e a /i/id picture o. the 3eha/iour o. the 6a/e .unctions, a simple description o. the
essence o. the .actors 6hich determine cohesion and an understanding o. the origins o. /ariation in
properties .rom metal to metal7G
A. 6e replace the 6ords metal, cohesi/e energy and lattice constant 3y molecule,
3inding energy and 3ond length respecti/ely, then this statement applies e0ually 6ell to
#,? The Co/alent Chemical Bond
'
n
e
r
g
y

(
e
8
+
(
W
i
t
h

r
e
s
p
e
c
t

t
o

i
n
.
i
n
i
t
e
l
y

s
e
p
a
r
a
t
e
d
,

s
t
a
t
i
o
n
a
r
y

p
r
o
t
o
n
s

a
n
d

e
l
e
c
t
r
o
n
s
+
'
n
e
r
g
y


#
0
#
$

(
J
+
(
W
i
t
h

r
e
s
p
e
c
t

t
o

l
o
6
e
s
t

e
l
e
c
t
r
o
n
i
c

e
n
e
r
g
y

o
.


9
2
+
the 0uantum2mechanical study o. molecules7 We no6 ha/e Qgreat calculating machinesG
6hich gi/e us much assistance in the application o. 0uantum mechanics, 3ut 6e are still
una3le to sol/e SchroM dingerGs e0uation in most cases o. chemical interest7 Wigner
and SeitKGs criteria remain as /alid today as they 6ere in #$55, and 6e shall 3ear them
/ery much in mind in this chapter7 And so to our Lrst simpli.ying approimation7
*1' THE 82RN I 2!!ENHEIMER A!!R2DIMATI2N
Ca Born and J7 :o3ert "ppenheimer (#$0* I #$?-+ 6ere among the Lrst to consider
the pro3lem o. applying SchroM dingerGs ne6 e0uation to molecules7 They recognised
that the mass o. the proton is #%,? times that o. the electron and that the nuclei there.ore
mo/e /ery much more slo6ly than the electrons7 Because o. this it should not 3e
necessary to treat 3oth types o. particle in eactly the same manner as the terms in our
9amiltonian operator a3o/e re0uire (compare '0uation (?727#+ 6ith '0uation (?7272+ and
'0uation (?727*+ 6ith '0uation (?7275++7 An #$2- they sho6ed 6ith a rigorous
mathematical analysis that only a /ery small error is introduced into the calculation
o. the electronic energy .or any particular internuclear distance (3ond length+ i. the
nuclei are held stationary at the 3ond length in 0uestion7 This remo/es the t6o nuclear
4inetic energy terms ('0uation (?727#++ .rom the 9amiltonian and the internuclear
repulsion 3ecomes a simple constant 6hich can 3e added in at the end7 The calculation
can then 3e repeated .or a num3er o. 3ond lengths and a graph o. 3ond length against
energy plotted in order to Lnd the minimum in the cur/e and the associated e0uili3rium
3ond length (R
e
+7
The type o. graph 6e epect to o3tain 3y this process is sho6n in Digure ?7,7 "n the
right o. the Lgure, 6here R is large, the cur/e o. energy against R is horiKontal7 This is
the region o. t6o non23onded hydrogen atoms 6here a change o. the internuclear distance
20 #2
#5
#%
#0
9
2 9 + 9
2*
5 E
e
E
0
,0
0
Nero2point energy
R
e
,?
50 #00 #50 200 250 ,00
Anternuclear distance (pm+
6ig;re *1' The hydrogen molecule1 energy vers1s internuclear distance
9eitler and London1 the 8alence Bond (8B+ Codel #,-
ma4es no di..erence to the electronic energy, 6hich is simply that o. the t6o hydrogen
atoms7 The energy at this point is 2-72#0 e8, as eplained in Section ?7#7
A. a sta3le molecule is to 3e .ormed, there must 3e a decrease in energy as 6e mo/e
to6ards smaller /alues o. R and this process 6ill continue until the mutual repulsion o.
the nuclei and o. the electrons 3egins to ma4e itsel. .elt and the energy 3egins to rise
againP normally 0uite steeply7 The energy di..erence 3et6een the minimum at R
e
and the
horiKontal cur/e at large R is E
e
and the 6hole cur/e can 3e constructed 3y calculating
the electronic energy o. t6o hydrogen atoms at a series o. /alues o. R7 The .act that 6e
are a3le to proceed in this 6ay, i7e7 the .act that the Born I "ppenheimer approimation
is such an ecellent one, has a signiLcance 6hich etends .ar 3eyond our present tas4 and
touches e/ery aspect o. chemistry7 "ne o. the most signiLcant ad/ances in chemistry in
the 20th century 6as the 6ay in 6hich 6e no6 thin4 o. molecules as three2dimensional
spatial entities7 The concept o. molecular shape and structure is no6 .undamental to our
understanding o. the 6ay in 6hich molecules interact and react chemically, and these
properties are also recognised to 3e /ital to ad/ances in su3@ects such as materials science
and molecular 3iology7 But i. the Born I "ppenheimer approimation could not 3e
made and the nuclei and electrons in a molecule had to 3e treated e/en2handedly,
then the motions o. the t6o sorts o. particles 6ould 3e inetrica3ly ent6ined7 And
there 6ould then 3e no 6ay in 6hich 6e could dra6 the comple structural .ormulae
upon 6hich 6e so much rely and 6hich are nothing more than representations o. the
e0uili3rium positions o. the nuclei o. the molecule7 A. the Born I "ppenheimer
approimation 6as not possi3le, then there 6ould also 3e no such thing as structural
chemistry as 6e 4no6 itU
8itally important though it is, the Born I "ppenheimer approimation still lea/es
us 6ith a lot o. 6or4 to do7 The 9amiltonian still contains se/en terms1
2 2 2
2

# # # # # #
h !
#
+
2
" e
9

=
(?7,7#+
%(
2
m

*( ?
0
r
A#
+
r
B#
+
r
A2
+
r
B2

r
#2

:
AB
and a direct solution o. the SchroM dinger e0uation is still impossi3le7
At this @uncture 6e recall the discussion, in Section *7$, o. the pro3lem o. calculating
an o3ser/a3le 0uantity .or a system 6hich is not in an eigenstate o. the appropriate
operator7 According to '0uation (,7$72+, a mean or epectation /alue o. the energy 6hich
6e re0uire can 3e .ound .or a normalised trial 6a/e .unction ( + using the e0uation1

E =

9

dv
#
dv
2
!?.,.2"
;ote that, since 6e no6 ha/e t6o electrons to consider, 6e ha/e to integrate o/er the
three spatial coordinates o. 3othP a total o. si integrations7 This is not a tri/ial calculationU
But, although 6e ha/e the 9amiltonian operator, 6e ha/e no 6a/e .unction7 9o6 can
6e proceedJ
*1( HEIT5ER AN3 52N32N: THE VA5ENCE 82N3 FV8G M23E5
An the Lrst success.ul calculation o. the energy o. a co/alent 3ond, Walter 9eitler
(#$0* I #$%#+ and DritK London (#$00 I #$5*+ proposed that an approimate 6a/e
.unction could 3e o3tained .rom our 4no6ledge o. the 6a/e .unctions o. the hydrogen
atom in the .ollo6ing manner7 We Lrst suppose that our t6o hydrogen atoms are .ar apart
6ith electron # in $
A
, the normalised #s atomic or3ital around nucleus A, and electron 2
in $
B
,
#,% The Co/alent Chemical Bond
James and CoolidgeP #,2term .unction *7-2 -75? -*70
>olos and :oothaanP 502term .unction *7-*?- -7?0*- -*7#
d
'perimental /alues *7-*?% -7?0*% -*7#
07000- 0700#
R
the #s or3ital around nucleus B7 The 6a/e .unction, G , .or this system o. t6o separated
hydrogen atoms 6ill 3e1
G
=
$
A
!#"

$
B
!2" !?.*.#"
;ote that the t6o #s .unctions are com3ined as a product 3ecause each is a pro3a3ility
.unction and the pro3a3ility o. t6o e/ents ta4ing place is the %rod1ct o. the pro3a3ilities
o. each o. the indi/idual e/ents ta4ing place7
;o6 imagine that the t6o atoms mo/e close enough together to .orm a 3ond7 Then 6e
might assume, to a Lrst approimation, that the a3o/e 6a/e .unction remains /alid7 This
is 6hat 9eitler and London suggestedP 3ut 6ith one important addition7 When the t6o
atoms .orm a 3ond the electrons occupy a common region o. space and can no longer
3e thought o. as conLned to one particular nucleus7 Durthermore, it is .undamental to the
0uantum theory that electrons are indistinguisha3le7 Thus, the alternati/e 6a/e .unction1
G = $
B
!#" $
A
!2" !?.*.2"
is e0ually suita3le, and .or a correct description o. the molecule 3oth are re0uired1

/3
= ;{$
A
!#" $
B
!2" + $
B
!#" $
A
!2"} !?.*.,"
We should also note that 6hen the t6o hydrogen atoms are 3rought together so that
the electrons occupy a common region o. space, then the !auli principle re0uires that the
spins o. the electrons must 3e paired and the a3o/e 6a/e .unction represents the interac2
tion o. t6o hydrogen atoms 6ith opposite electron spins7 The inter2relationship 3et6een
the spin and the spatial distri3ution o. electrons raises many etremely important 0ues2
tions 3ut, .ortunately, 6e need only the spatial parts o. the 6a/e .unctions .or our present
Ta?le *1% A summary o. some o. the calculations on the hydrogen molecule
Type o. 6a/e .unction E
e
a
*
e
He8 ,J #0

#$
Hpm
Simple /alence 3ond (N = #+ ,7#* 570, %?7$
Simple molecular or3ital (N = #+ 27?% *72$ %570
8B 6ith N = #.#?? ,7-% ?70? -*7,
C" 6ith N = #.#$- ,7*$ 575$ -,72
8B + polarisation (N = #.#-, N = 0.#2,+ *702 ?7** -*70
H!co/alent" + <H !ionic" !< 0.25" *705 ?7*$ -*7$
Best calculation 6ithout eplicit inclusion o.
electron correlation
*72- ?7%* -*70
c
a
<issociation energy per molecule
*
'0uili3rium 3ond length
c
Calculated .or this /alue o. : only7
d
An #$?%, >olos and Wolnie6icK reported a calculation using a #002term .unction7
Generally, 3ut not al6ays 3ecause o. the hea/y calculations in/ol/ed, each successi/e, impro/ed calculation
incorporates the impro/ements made in earlier 6or47 An etensi/e re/ie6 o. the early calculations on the
hydrogen molecule may 3e .ound in the paper 3y A7<7 CcLean, A7 Weiss and C7 Roshimine, Rev. 5od. Phys.,
'&, 2## (#$?0+7
9und and Culli4en1 the Colecular "r3ital (C"+ Codel #,$
purposes so, .or the moment, 6e postpone the additional complication o. spin7 "ne aspect
o. the space2spin pro3lem is eplored in Bo ?7* and the su3@ect is discussed more thor2
oughly in Section ##757 The .actor ; has 3een introduced to normalise the 6a/e .unction
'0uation (?7*7,+ (Bo ?7#+7 Anserting the 6a/e .unction
/3
into '0uation (?7,72+ ena3led
9eitler and London to calculate the epectation /alue o. the energy, E, and 3y /arying R,
to Lnd an energy minimum and a /alue .or the e0uili3rium 3ond length o. the hydrogen
molecule7 The calculated energy o. ,7#* e8 and 3ond length o. %?7$ pm do not compare
/ery 6ell 6ith the eperimental /alues o. *7-* e8 and -*7# pm (Ta3le ?7#+7 9o6e/er, the
result represented an enormous ad/ance on the pre/ious position and, moreo/er, it 6as
immediately clear ho6 the 6a/e .unction could 3e reLned, there3y impro/ing the result7
But 3e.ore 6e consider the possi3le impro/ements 6e should introduce another .orm o.
6a/e .unction, a concept 6hich 6as suggested 3y Driederich 9und (#%$? I + and
:o3ert Sanderson Culli4en (#%$? I #$%?+ among others7
*1) HUN3 AN3 MU55I=EN: THE M25ECU5AR 2R8ITA5
FM2G M23E5
9und and Culli4en approached the pro3lem o. Lnding a suita3le 6a/e .unction .or 9I9
in a rather di..erent 6ay7 The solutions o. SchroM dingerGs e0uation .or the hydrogen
atom, the atomic or3itals, may 3e regarded as regions o. space 6hich can 3e occupied
3y one or t6o, 3ut not more, electrons7 9und and Culli4en suggested that one might
en/isage similar regions o. space surrounding not one 3ut t6o (or more+ nuclei7 These they
called molecular or3itals and .or the hydrogen molecule they suggested the .ollo6ing
.orm1
G
mo
= ;

{$
A
+ $
B
} !?.5.#"
There are important points to 3e made a3out this 6a/e .unction7 The .actor ;

is again
a normalising constant (Bo ?7#+7 The atomic or3ital .unctions are the normalised #s .unc2
tions o. nuclei A and B as 3e.oreP 3ut note that there is, as yet, no mention o. the electrons7
At is .or this reason that 6e ha/e a sum o. the t6o .unctions rather than a product7 At this
stage 6e are concerned merely to esta3lish a .orm .or the molecular or3ital 6hich 6e
shall later populate 6ith t6o spin2paired electrons7 As 6ith the 9eitler I London
.unction, the 9und I Culli4en .unction ('0uation (?757#++ is an approimation7 The
@ustiLcation .or its .orm is solely that 6e 4no6 that the .unctions $
A
and $
B
are the eact
atomic or3itals an electron occupies 6hen it is in the region o. a single hydrogen
nucleus, remote .rom all other atoms7 9und and Culli4enGs .unction simply assumes that
this remains the case 6hen t6o such atoms approach to 6ithin 3onding distance7 The
calculation 6ill sho6 @ust ho6 /alid this assumption is7 We must no6 introduce the
electrons into our molecular or3ital7 Both can 3e accommodated in the one or3ital i.
they ha/e opposite spins and 6e 6rite1

mo
=
G
mo
!#"

G
mo
!2" !?.5.2"
The calculation 6ith the 9und and Culli4en .unction gi/es a 3inding energy o. 27?% e8
and a 3ond length o. %570 pm (Ta3le ?7#+7 This result is mar4edly in.erior to that o. 9eitler
and London, 3ut the molecular or3ital method o. o3taining a 6a/e .unction has pro/ed to
3e one o. the most .ruit.ul concepts in the application o. 0uantum mechanics to chemical
pro3lems, as 6e shall see7
#*0 The Co/alent Chemical Bond
*1* IM!R2VIN THE 4AVE 6UNCTI2NS
The results o. the early calculations 6ere /ery encouraging, 3ut it 6as clear that impro/e2
ments 6ere re0uired and directions 6hich these should ta4e 6ere rapidly recognised7 The
Lrst impro/ements suggested .or 3oth 6ere the same and they are important not only
3ecause they gi/e 3etter numerical results .or the calculation o. the 9I9 3inding energy,
3ut also .or the physical insight 6hich they 3ring to the pro3lem7 But 3e.ore 6e em3ar4
upon a 3rie. description o. that 6or4 6e need to address an important pro3lem1 6hat is
the criterion 3y 6hich 6e shall @udge the impro/ement, or lac4 o. itJ
The o3@ect o. the calculation is to determine the energy o. the hydrogen molecule 6hich
lies mar4edly lo6er than the simple calculations predict, i7e7 the calculated /alue o. E
e
is
smaller than the eperimental /alue7 At seems natural, there.ore, to suggest that the lo6er
our calculated energy the 3etter the 6a/e .unction7 But is there not a danger that 6e
might choose a 6a/e .unction that predicts an energy lo6er than the eperimental /alue,
and 6hat 6ould such a result implyJ Dortunately, this dilemma 6ill not trou3le us7 A
theorem 4no6n as the /ariation theorem, 6hich is pro/ed and applied to another pro3lem
in Appendi 2, sho6s that no legitimate 6a/e .unction .or any 0uantum2mechanical
pro3lem can gi/e an energy 6hich is less than the true lo6est energy eigen/alue o. the
system 6hich it descri3es7 There.ore, 6e can modi.y our C" and 8B 6a/e .unctions in
any reasona3le 6ay, conLdent that the closer 6e get to the eperimental energy the 3etter
is our calculation and the 6a/e .unction used7
*1*1% T$e Aal;e o" :
An the isolated hydrogen atom the electron mo/es under the electrostatic attraction o. a
single nucleus, 3ut in the molecule it mo/es in the Leld o. t6o nuclei7 Though it may not
.eel t6ice the attracti/e .orce 6hich it does in the atom, on account o. the screening e..ect
o. the other electron and the .act that the t6o nuclei are not coincident, it is, ne/ertheless,
to 3e epected that an electron 6ill 3e dra6n in more closely to the t6o nuclei than it is
in the atom7 9o6 can this 3e allo6ed .or in the 6a/e .unctionJ
The alge3raic epression .or the normalised #s atomic or3ital (A"+ o. the hydrogen
atom is (Appendi 5+1
#
$
=
(
,

N

2
a
0
ep

Nr

a
0
!?.?.#"
9ere, a
0
is the Bohr radius, r is the distance 3et6een the electron and the proton and N
represents the charge on the nucleus in units o. the charge on the proton7 An the isolated
hydrogen atom N = #7 At 6as suggested 3y S7C7 Wang that the increase in the attraction
to the nuclei .elt 3y electrons in the hydrogen molecule as opposed to the hydrogen atom
implied an increase in the /alue o. N, 6hich 6ould ha/e the e..ect o. dra6ing the A"s $
A
and $
B
a little closer around their respecti/e nuclei7 An #$2% detailed calculations sho6ed
that increasing N did indeed produce impro/ed /alues o. E
e
and R
e
(Ta3le ?7#+ and the
3est /alues o. N 6ere .ound to 3e #7#?? and #7#$- .or the 8B and C" 6a/e .unctions
respecti/ely7
*1*1& !olarisation
An #$,#, ;7 :osen noted that the presence o. another nucleus at the side o. each #s A"
6ould 3e epected to distort that A" .rom the pure spherical shape it 6ould ha/e in
F

(
a
0
+
=niLcation1 Aonic Structures and ConLguration Anteraction #*#
,
2
07#0
#
0720
07,0
0
0725
#
07#5
2
0705
,
, 2 # 0 # 2 ,
N (a
0
+
6ig;re *1( !olarisation o. the hydrogen #s A" 3y addition o. 2p
K
an isolated atom7 9e proposed that this e..ect could 3e allo6ed .or 3y 3uilding a 8B
or C" 6a/e .unction .rom a composite atomic 6a/e .unction centred on each nucleus7
The ma@or contri3utor to the .unction 6ould 3e the #s A" as 3e.ore, 3ut there 6ould 3e
a small addition o. a 2p A" pointing in the direction o. the other nucleus7 ;eglecting
normalising .actors and choosing the K2direction as the internuclear ais, the polarised
atomic .unction, $

, 6ould 3e o. the .orm1
$

= Z$
#s
+ N $
2p
K
\ !?.?.2"
N is simply a num3er 6hich, in accordance 6ith the /ariation theorem, is to 3e /aried
until the lo6est energy (greatest 3inding energy+ is .ound7 Because or3itals ha/e a phase,
the positi/e com3ination o. a #s and a 2p
K
or3ital produces a .unction 6hich has a larger
electron pro3a3ility in the positi/e K2direction than in the negati/e7 Thus, the electron
density is no longer spherically symmetrical 6ith respect to the nucleus 3ut is polarised
in the positi/e K2direction 6hich is @ust 6hat 6e re0uire7 The distortion is illustrated in
Digure ?7* .or N = 0.#57 The other 9 atom can 3e polarised in the negati/e K2direction
3y .orming the negati/e com3ination o. #s and 2p
K
7 :osen carried out a calculation 3ased
on the 8B 6a/e .unction plus polarisation and .ound the impro/ed /alues o. E
0
and R
e
sho6n in Ta3le ?7#7 The 3est /alue o. N 6as 07#2, (#75 Y o. $
2p
K
+ .or N
=
#.#-7
*1+ UNI6ICATI2N: I2NIC STRUCTURES
AN3 C2N6IURATI2N INTERACTI2N
The impro/ements in the 6a/e .unction suggested 3y Wang and :osen ha/e a /ery clear
physical 3asis in the mutual electrostatic attraction o. positi/e and negati/e charges7 They
sho6 us that, e/en in the realms o. 0uantum mechanics, simple electrostatic reasoning can
still 3e applied 6ith /ery 3eneLcial results7 An .act, as 9ellmann and Deynman indepen2
dently pro/ed, 6e re0uire SchroM dingerGs e0uation to determine the electron
distri3ution
#*2 The Co/alent Chemical Bond
in a 0uantum2mechanical system 3ut once 6e ha/e that distri3ution 6e can calculate the
potential energy using classical electrostatics7
9o6e/er, in spite o. the great success o. the theory thus .ar, 6e are still some 6ay .rom
the le/el o. agreement 3et6een theory and eperiment 6hich 6e re0uire to pro/e that
0uantum mechanics is the theory 6hich interprets the chemical 3ond 0uantitati/ely7 And
more importantly, 6e ha/e t6o models, the C" and the 8B7 The t6o di..erent methods
cannot 3e simultaneously correct unless they can 3e sho6n to 3e di..erent .ormulations
o. the same theory7 An #$,, S7 Wein3aum 3rought the C" and 8B approaches together
in the .ollo6ing manner 6hich, again, has a strong 3asis in simple physical2chemical
reasoning7
We Lrst 6rite out the simple 8B .unction o. 9eitler and London ('0uation (?7*7,++,
neglecting the normalising constants1

/3
= $
A
!#" $
B
!2" + $
B
!#" $
A
!2" !?.-.#"
The simple, un2normalised C" 6a/e .unction ('0uation (?7#*++ is1

mo
= Z$
A
+ $
B
\!#" ZZ$
A
+ $
B
\!2"
Z$
A
!#" + $
B
!#"\ Z$
A
!2" + $
B
!2"\ (?7-72+
At can 3e multiplied out in eactly the same 6ay as the product o. t6o 3rac4ets in
alge3ra gi/ing .our terms1

mo
= $
A
!#" $
A
!2" + $
B
!#" $
B
!2" + $
A
!#" $
B
!2" + $
B
!#" $
A
!2"
(?7-7,+ We note that the last t6o terms o. this .unction are eactly the same as those
o. the
8B .unction 6ith the electrons in di..erent A"s, 6hile the Lrst t6o terms ha/e either
3oth electrons in the A" $
A
or 3oth in $
B
7 The physical meaning o. the /arious terms
is clear7 Those contri3utors to the 6a/e .unction in 6hich 3oth A"s are occupied 6ith
one electron each distri3ute the t6o electrons o/er the molecule as one 6ould epect in
a co/alent 3ond7 The other t6o terms place 3oth electrons in the region o. one nucleus
so that the molecule is negati/ely charged at one end and positi/ely charged at the other7
This is an ionic structure, 9
+
I9

, and 6e see that the C" 6a/e .unction consists o.


ionic and co/alent structures in e0ual proportions ('0uation (?7-7*++1

mo
= H !co/alent" + H !ionic" !?.-.*"
6hereas the 8B 6a/e .unction has only co/alent structures7 Drom our 4no6ledge o.
chemistry, 6e do not epect ionic 3onding to play a /ery important role in the structure
o. 9I9, though it may 6ell do so in the case o. a molecule such as 9ID, 6here there
is a large di..erence in the electronegati/ities o. the t6o atoms in/ol/ed7 At there.ore
seems li4ely that the C" theory o/er2emphasises the importance o. ionic contri3utions
to the 3onding and it might 6ell impro/e the 6a/e .unction i. a 6ay could 3e .ound
o. reducing the importance o. these ionic terms7 An the same /ein, although 6e epect
the contri3utions o. the ionic terms to the 3onding to 3e small, it 6ould impro/e the
8B .unction i. 6e could add a small proportion o. ionic structures to the purely co/alent
description 6hich 6e currently ha/e7 Wein3aum did this 3y 6riting the 8B 6a/e .unction
as a sum o. co/alent and ionic terms in the .orm1

/3
= H !co/alent" + <H !ionic" !?.-.5"
'lectron Correlation #*,
and /arying < to Lnd the maimum E
e
7 The /alue o. < .ound 6as in the region o. 0725,
the eact Lgure 3eing determined 3y the /alues o. the other /aria3le parameters in/ol/ed,
i7e7 N and N 7 At should 3e noted that this is a /ery hea/y calculation indeed, in that the
e..ects o. screening and polarisation ha/e also to 3e considered since the /alues o3tained
.rom earlier calculations cannot 3e ta4en o/er unchanged into a di..erent 6a/e .unction7
We sa6 this earlier 6hen t6o di..erent /alues o. N 6ere .ound .or the C" and 8B 6a/e
.unctions (Section ?7?7#+7
At this point it is natural to as4 6hat change might 3e made to the C" 6a/e .unction
to impro/e it 3y reducing the contri3ution o. the ionic terms7 The ans6er lies in the
out2o.2phase com3ination o. the hydrogen #s atomic or3itals 6hich, as 6e shall see in
Section ?7$, represents a higher energy state o. the hydrogen molecule7 We place the t6o
electrons in this higher2energy C" 6ith the t6o spin2paired electrons eactly as 6e did
in '0uation (?7-72+ and 6rite the simple, un2normalised C" 6a/e .unction,

mo
, as1

mo
= Z$
A
$
B
\!#" ZZ$
A
$
B
\!2"

Z$
A
!#"

$
B
!#"\

Z$
A
!2"

$
B
!2"\ (?7-7?+
At can 3e multiplied out in the same 6ay as 3e.ore gi/ing1

mo
= $
A
!#" $
A
!2" + $
B
!#" $
B
!2" $
A
!#" $
B
!2" $
B
!#" $
A
!2"
(?7-7-+ We see immediately that the co/alent terms no6 carry a negati/e sign so
that in a
com3ined C" 6a/e .unction, , o. the .orm1
=
mo
T

mo
!?.-.%"
The /alue o. T can 3e used to decrease the contri3ution o. the ionic terms @ust as < 6as
used in the 8B 6a/e .unction ('0uation (?7-75++ to increase it7 The procedure 6here3y a
6a/e .unction is impro/ed 3y the addition o. another arrangement o. electrons in or3itals,
i7e7 another conLguration, is 4no6n as conCg1ration interaction7 The 8B 6a/e .unction
6ith the addition o. ionic terms and the C" 6a/e .unction 6ith conLguration interaction
can 3e made identical 6ith suita3ly chosen /alues o. < and T7 With Wein3aumGs 6or4
uniLcation 6as complete and the t6o approaches to the pro3lem had con/erged, as they
must do i. they are descri3ing the same truth7 But the calculated /alue o. E
e
6as still
only %5 Y o. the eperimental /alue and this 6as not good enough to pro/e that 0uantum
mechanics pro/ides a 0uantitati/e description o. the co/alent 3ond7 Something more 6as
re0uired and it 6as pro/ided 3y 97C7 James and A7S7 Coolidge 6ho recognised the
pro3lem o. electron correlation7
*1, E5ECTR2N C2RRE5ATI2N
An reLning the 6a/e .unctions used to descri3e the hydrogen molecule, :osen realised
that the presence o. nucleus A 6ould polarise (distort+ the spherically symmetrical #s
electron distri3ution around nucleus B and /ice /ersa (Digure ?7*+7 This is essentially a
static distortion, 3ut there is another, dynamic distortion process that is caused 3y the
mutual repulsion o. the t6o electrons, 6hich there.ore mo/e in such a 6ay as to reduce
this repulsion7 They a/oid each other7 This e..ect upon their motion is 4no6n as electron
correlation7 James and Coolidge sho6ed that this e..ect must 3e eplicitly allo6ed .or, not
@ust in the 9amiltonian operator as in '0uation (?7,7#+, 3ut also in the 6a/e .unction itsel.7
#** The Co/alent Chemical Bond
'
l
e
c
t
r
o
n
s

p
e
r

=
n
i
t

L
e
n
g
t
h

(
e
H
a
0
+
An a .ormida3le calculation, 6ithout the aid o. a computer and using a 6a/e .unction that
6as the sum o. #, terms, they o3tained E
e
= *.-2 e8 and R
e
= -*.0 pm7 This /alue o.
E
e
is $$7* Y o. the eperimental /alue and this impressi/e result le.t little room .or dou3t
concerning the applica3ility o. 0uantum mechanics to the pro3lem o. the chemical 3ond7
An #$?0 >olos and :oothaan repeated the James and Coolidge calculation 6ith a
502term .unction and o3tained a result that agrees 6ith eperiment to 6ithin eperimen2
tal accuracy (Ta3le ?7#+7 An .act, the result is 3etter than it should ha/e 3een 3ecause
the Born I "ppenheimer approimation, though good, is not that good7 The
eceptional agreement o. theory and eperiment is attri3uted to a .ortunate cancellation o.
the small errors due to the Born I "ppenheimer approimation in this particular
pro3lem7 An /ery recent years calculations 6hich do not in/o4e the Born I "ppenheimer
approimation at all ha/e 3een carried out7 The results completely conLrm the positi/e
conclusions a3o/e and today 6e do not dou3t that 0uantum mechanics pro/ides a
0uantitati/e theoretical model o. the chemical 3ond in all its .orms7
But as Wigner and SeitK so clearly recognised, a 6a/e .unction composed o. 50 terms is
not a /ery /isual thing and 6e need a more pictorial description o. the 3ond7 An Digure ?75
6e attempt to pro/ide this picture7 The horiKontal ais o. the Lgure runs through the t6o
hydrogen nuclei 6hich are sho6n as t6o dots at

0.-0 a
0
7 The /ertical ais gi/es the
num3er o. electrons that can 3e .ound 6ithin a disc o. inLnite radius and # a
0
thic4 at right2
angles to the internuclear ais7 The continuous lines are the graphs .or the A"s $
A
and
$
B
centred on the t6o protons as they 6ould 3e i. there 6ere no interaction 3et6een the
t6o hydrogen atoms7 The area under each graph is e0ui/alent to one electron7 The dotted
line is the graph corresponding to the most simple C" 6a/e .unction ('0uation (?7#7#*++
3ut multiplied 3y t6o so that the area 3eneath it is e0ui/alent to t6o electrons and is
there.ore directly compara3le 6ith the sum o. the areas under the t6o A" plots7 We see
that the electron density in the 3onding C" is greater in the internuclear region than the
sum o. the t6o A" densities7 This is a direct result o. the .act that the electron density is
gi/en 3y the s0uare o. the 6a/e .unction so that !$
A
+
$
B
"
2
is greater than !$
A
"
2
+
!$
B
"
2
3ecause o. the presence o. the cross2term, 2$
A
$
B
, in the .ormer7 The increased electron
density in the internuclear region dra6s the nuclei together and is the primary cause o. the
07%
07?
07*
072
070
? * 2 0 2 * ?
Anternuclear Ais (a
0
+
6ig;re *1) 'lectron distri3ution in the 3onding molecular or3ital o. the hydrogen molecule
'
l
e
c
t
r
o
n
s

p
e
r

=
n
i
t

l
e
n
g
t
h

(
e
H
a
0
+
Bonding and Anti3onding C"s #*5
9I9 3ond7 9ere again 6e see that, once 0uantum mechanics has 3een used to determine
electron distri3ution, 6e can understand the .orces acting 3et6een the /arious particles
.orming a molecule using classical electrostatics7 :ecall at this point that the data 6e
ha/e plotted are dra6n .rom the most simple C" 6a/e .unction, 6hich gi/es a rather
poor 3inding energy7 Allo6ing .or the polarisation o. the 3asic #s A"s and a reduction
in importance o. the ionic terms, as descri3ed a3o/e, increases the di..erence 3et6een the
C" electron density and the sum o. the t6o A" densities in the internuclear region and
outside it7
*1- 82N3IN AN3 ANTI82N3IN M2s
An the a3o/e interpretation o. the origin o. the co/alent hydrogen 3ond 6e noted that,
as a result o. the cross2term +2$
A
$
B
, 6hich arises .or the C" 6a/e .unction ('0ua2
tion (?757#++, there 6as a 3uild2up o. electronic charge 3et6een the t6o protons7 But i.
6e had chosen to .orm a molecular or3ital 3y ta4ing the A" com3ination $
A
$
B
, 6e
6ould ha/e .ound a negati/e cross2term, 2$
A
$
B
, and a conse0uent dimunition o. charge
in the internuclear region7 Let us call these t6o possi3ilities G
+
and G

i7e71
G
+
= ;
+
{$
A
+ $
B
} (?757#a+
G

= ;

{$
A
$
B
} (?7$7#+
But 6hy should 6e e/en consider the possi3ility o. com3ining the t6o A"s 6ith
opposite signs, i7e7 o. ta4ing the out2o.2phase com3inationJ There is more than one ans6er
to this 0uestion, 3ut one o. the most important is that such an C" is 4no6n .rom
eperiment to eist7 When the hydrogen molecule is irradiated 6ith light o. a 6a/elength
in the region o. ##0 nm ($

#0
%
cm

#
+ it a3sor3s that light and is ecited to a higher
energy state that has 3een sho6n 3y spectroscopic studies to 3e a state in 6hich the C"
G
+
contains one electron and the C" G

one electron7
A graph o. the C" G

o. the same .orm as Digure ?75 is sho6n in Digure ?7?7 We no6
ha/e a situation in 6hich the electron density in the internuclear region is much reduced
07%
07?
07*
072
070
? * 2 0 2 * ?
Anternuclear Ais (a
0
+
6ig;re *1* 'lectron distri3ution in the anti3onding C" o. the hydrogen molecule
#*? The Co/alent Chemical Bond

(3ecause o. the negati/e cross2term+ compared 6ith the sum o. the t6o A" densities7
Andeed, since the A"s are com3ined 6ith opposite phases, the electron density must 3e
eactly Kero mid26ay 3et6een the nuclei7 C"s o. this type are called anti3onding C"s
since electrons occupying them cause the atoms to separate rather than to .orm a 3ond7
This means that molecules 6ith electrons in anti3onding or3itals are unsta3le and reacti/e
and they .re0uently decompose or enter into chemical reactions7 The a3sorption o. light is
the most common cause o. electrons entering anti3onding C"s and the chemical reactions
6hich then ensue are called photochemical reactions7 The most important photochemical
reaction is the process o. photosynthesis 6hich ta4es place in green plants7 Another
important, 3ut less 3eneLcial, one is the primary reaction in the se0uence 6hich generates
photochemical smog1
;"
2
!gas" + h> ;"(gas+ + "(gas+
*1%. 4HY IS THERE N2 HEIHE 82N37
When 6e recognise that anti3onding as 6ell as 3onding C"s eist, an eplanation o. the
.act that there is no helium (9eI9e+ molecule is /ery clear7 Consider the energy le/el
scheme (Digure ?7-(3++, 6hich is 0ualitati/ely the same as that .or 9I9 (Digure ?7-(a++,
apart .rom the .act that 6e no6 ha/e .our electrons to 3e placed in the a/aila3le C"s7
Both 3onding and anti3onding C"s are no6 .ull and 3onding and anti3onding .orces are
0uite e/enly 3alanced7 An .act, more sophisticated calculations sho6 that the anti3onding
eceeds the 3onding and no sta3le helium molecule can 3e .ormed7
*1%% AT2MIC 2R8ITA5 2VER5A!
An the last section, the sign and magnitude o. the cross2term generated 6hen a C" 6a/e
.unction is s0uared 6as seen to 3e a /ery important criterion in the description o. a
co/alent 3ond7 A large positi/e term places a large electron density 3et6een the nuclei
dra6ing them to6ards it to .orm a 3ond, 6hile a large negati/e term remo/es electron
density .rom 3et6een the nuclei 6hich then ha/e nothing to pull them together7 :ather,
the mutual repulsion o. their positi/e charges, lac4ing the screening o. an intermediate
electron cloud, dri/es the nuclei apart7
The nature o. the cross2term is such that it only has a /alue in those regions o. space
6here 3oth $
A
and $
B
each ha/e a signiLcant /alue, i7e7 in the region 6here the t6o
A"s overla%7 Dor this reason 6e call $
A
$
B
an or3ital o/erlap and it plays a central role
Anti23onding s
molecular or3ital
;on2interacting 9

#s atomic or3itals

Anti23onding s
molecular or3ital
;on2interacting 9e

#s atomic or3itals

(a+
Bonding s molecular
or3ital

(3+
Bonding s molecular or3ital
6ig;re *1+ Colecular or3ital energy2le/el schemes .or 9
2
and 9e
2
Atomic "r3ital "/erlap #*-
in 0ualitati/e discussions o. 3onding in 3oth diatomic and polyatomic molecules7 Apart
.rom its sign, the o/erlap is characterised 3y its symmetry 6ith respect to rotation a3out
the internuclear ais in the .ollo6ing 6ay7
*1%%1% ' FsigmaG oAerlap
' o/erlap is cylindrically symmetrical 6ith respect to rotation a3out the internuclear ais
(Digure ?7%(a++7 That is, i. 6e /ie6 the 3ond .rom one end along the internuclear ais then
a rotation o. the molecule causes no apparent change in 6hat 6e see7 Both the positi/e and
the negati/e $
A
$
B
o/erlap in the hydrogen molecule are o. this type and 6e distinguish
them 3y using a

to indicate the anti3onding o/erlap7 We also add in.ormation a3out the
atomic or3itals in/ol/ed in the o/erlap and spea4 o. ' (#s+ and ' (#s+

o/erlap or '
(#s+
3onds and ' (#s+

anti3onds7
Cylindrically symmetrical o/erlap can also arise 6hen p2A"s o/erlap 6ith s2A"s
or 6ith other p2A"s, as illustrated in Digure ?7%(a+7 Typical descriptions o. this type
o. o/erlap are ' (#s22p+ or ' (2p+

7 Generally, since it is strongly directed along the


internuclear ais, ' o/erlap produces the strongest 3onds and the strongest anti3onds7
That is, the decrease in energy 6hen a ' 3ond is .ormed is larger than 6hen other
types o. 3onds are .ormed and the increase in energy 6hen a '

anti3ond is .ormed is
correspondingly greater7
*1%%1& ( FpiG oAerlap
When t6o A"s o/erlap in such a 6ay that rotation a3out the internuclear ais produces
a change o. sign e/ery #%0

then the o/erlap is termed ( o/erlap (Digure ?7%(3++7 A
s o/erlap
+ +
+
+
s (#s2#s+ s (#s2#s+S
s (#s22p+S

+ +
+ +
s (2p22p+ s (2p22p+S
(a+
p o/erlap
+ +
+
+ +


+ +
p (2p22p+ p (2p22p+S p (2p2,d+
(3+
6ig;re *1, ' ( ) and non23onding A" o/erlap
#*% The Co/alent Chemical Bond
y
d o/erlap
d (,d2,d+
(c+
d (,d2,d+S
non23onding o/erlap
+
+ +

+

(#s22p+ (2p22p+
(d+
;ote1 An Digure ?7%(c+ shading has 3een used to indicate phase in order to ma4e
the relati/e positions and orientations o. the t6o d

y
2
or3itals clear7
6ig;re *1, (contin1ed +
good eample is the o/erlap o. t6o 2p2A"s 6hich are orientated at right2angles to the
internuclear ais, as in the car3on2car3on ( 3ond in ethene7 The

to denote anti3onding
is also used and in ethene 6e ha/e ( (2p+ 3onding and ( (2p+

anti3onding interactions7
( (2p2,d+ is a rather special case o. o/erlap 3et6een p and d A"s 6hich is important in
organometallic chemistry and in the phosonitrilic compounds7
*1%%1' ) F/eltaG oAerlap
A. t6o nd
y
or nd

2
2
A"s 6ith their nuclei on the K ais are 3rought together, .ace2to2
.ace so to spea4, then they o/erlap in such a 6ay that rotation a3out the internuclear ais
produces a change o. sign e/ery $0

7 Such o/erlap is termed ) o/erlap (Digure ?7%(c++


and 6e can ha/e 3onding )(,d+ and anti3onding )(,d+

interactions7 This .orm o. o/erlap
plays an important role in some metal2metal 3onds, usually 6ith n R ,7
*1%%1( Non9?on/ing oAerlap
Apart .rom the eamples o. 3onding and anti3onding o/erlap 6e ha/e descri3ed a3o/e,
it is also possi3le .or A"s to o/erlap in such a 6ay that there is no interaction 3et6een
them7 An eample o. this non23onding o/erlap can 3e seen in Digure ?7%(d+ 6here the
o/erlap o. a 2s A" o. atom A 6ith a 2p A" o. atom B is illustrated7 The 2p A" is
orientated at right2angles to the internuclear ais and there are e0ual and opposite regions
o. o/erlap 3et6een the t6o A"s7 The 3onding and anti3onding interactions 3et6een them
The 9omonuclear <iatomic Colecules .rom Lithium to Dluorine #*$
Ta?le *1& Atomic #s, 2s and 2p or3ital o/erlap and 3onding
The o/erlapping
atomic or3itals
Type o. 3ond
a
Bonding or
anti3onding
#s + #s ' Bonding
#s

#s '

Anti3onding
2s + 2s ' Bonding
2s

2s '

Anti3onding
2s
+
2p
K
' Bonding
2s

2p
K
'

Anti3onding
2p
K
+
2p
K
' Bonding
2p
K

2p
K
'

Anti3onding
2p

+
2p

( Bonding
2p


2p

(

Anti3onding
2p
y
+
2p
y
( Bonding
2p
y

2p
y
(

Anti3onding
2s + 2p

non23onding
*
2s + 2p
y
non23onding
*
2p

+ 2p
y
non23onding
*
2p

+ 2p
K
non23onding
*
2p
y
+
2p
K
;on23onding
*
a
The internuclear ais is the K2ais7
*
;on23onding o/erlap does not depend upon the sign o. the or3ital
com3ination7 An2phase (++ and out2o.2phase (+ com3inations are
3oth non23onding7
cancel eactly and the total interaction 3et6een the t6o A"s is Kero7 At is important to
recognise that not all the A"s o. an atom can necessarily ta4e part in the .ormation o.
chemical 3onds or anti3onds, e/en 6hen their spatial distri3utions o/erlap7 The possi3le
o/erlaps and 3onding 3et6een #s, 2s and 2p A"s are summarised in Ta3le ?727
*1%& THE H2M2NUC5EAR 3IAT2MIC M25ECU5ES
6R2M 5ITHIUM T2 65U2RINE
At is much easier to construct simple, 0ualitati/e energy2le/el schemes .or molecules 6ith
the C" model than 6ith the 8B7 An constructing such schemes to descri3e the 3onding in
the a3o/e molecules 6e must ta4e account not only o. the relati/e magnitudes and signs
o. the o/erlap, 3ut also o. the relati/e energies o. the #s, 2s and 2p atomic or3itals o.
the elements in 0uestion7 The #s al6ays lies 6ell 3elo6 the 2s in energy and the 2s and
2p ha/e e0ual energies in the case o. hydrogen and mo/e .urther apart as 6e go to6ards
Ouorine7 The situation is .urther complicated 3y the .act that, as 6e ha/e seen a3o/e, 2s
and 2p A"s can interact i. the latter are orientated along the internuclear ais7 The most
important e..ect o. these changes in the relati/e energies o. the 2s and 2p A"s and the
2s22p ' interaction is that the order o. E!( #" and E!' ," changes (Digure ?7$+ and 6e
re0uire t6o energy2le/el diagrams, one .or the molecules lithium to nitrogen and another
.or oygen and Ouorine7 Coulson
,
and Currell, >ettle and Tedder
?
ha/e good discussions
o. these points7
But once 6e ha/e constructed suita3le energy le/el schemes, it is /ery easy to determine
the electronic conLgurations o. the molecules in 0uestion7 We simply Lll the C"s 6ith the
#50 The Co/alent Chemical Bond
s
;itrogen
s
*
"ygen
s
*
p
2
p
2
2p
s
,
2p
p
#
p
#
,
s
2
2s
s
2
s
#
2s
(a+
s
#
(3+
Lithium to nitrogen
"ygen and .luorine
6ig;re *1- Colecular or3ital energy2le/el schemes .or homonuclear diatomic molecules o. the
Lrst ro6 o. the periodic ta3le
a/aila3le electrons starting 6ith the lo6est (au.3au or 3uilding2up principle+ and placing
t6o, 3ut not more than t6o, electrons (!auli principle+ in each C"7 This is illustrated
.or nitrogen in Digure ?7$(a+ and .or oygen in Digure ?7$(3+7 The concept o. 3onding
and anti3onding o/erlap allo6s us to dra6 conclusions a3out the strength o. the 3ond
@oining the t6o atoms7 An the case o. nitrogen, .or eample, the #s2#s ' 3onding is /ery
small 3ecause the t6o #s A"s are /ery close to their respecti/e nuclei and their o/erlap
is almost Kero7 Thus, no 3onding (or anti3onding+ results .rom these .our core electrons7
The ' (2s+ 3onding o. C" '
#
, is e..ecti/ely cancelled 3y the ' (2s+

anti3onding o.
C"
'
2
, so no 3ond results .rom the .our electrons 6hich 6e place in these t6o C"s7 The
2p

22p

and 2p
y
22p
y
3onding interactions produce t6o 3onding ( C"s o. e0ual
energy
((
#
degenerate+ and they can accommodate .our electrons7 'ach dou3ly2occupied 3onding
C" constitutes one 3ond so 6e ha/e t6o 3onds7 Dinally, the last t6o electrons can 3e
placed in the 3onding ' C" .ormed 3y the 2p
K
22p
K
o/erlap, '
,
7 They pro/ide one more
3ond .or the molecule 6ith the result that 6e ha/e a /ery strong ;

; triple 3ond, in
agreement 6ith the usual description o. the molecule7 '
2
contains a little 2p
K
and '
,
a
little 2s, 3ut the sHp miing is small 3ecause o. the large E
2s
,E
2p
energy gap7
Dor the oygen molecule 6e proceed in the same 6ay until 6e come to the point 6here
only t6o electrons remain to 3e placed in C"s7 The C"s net in energy are a pair o.
degenerate (

C"s ((
2
+ and, .ollo6ing 9undGs rule, 6e must place one electron in each
o. these C"s and the spins o. the t6o electrons must 3e the same7 The result o. this
parallel orientation o. t6o electron spins is that theory predicts that the oygen molecule
9eteronuclear <iatomic Colecules #5#
is paramagnetic (Section #272+ and this is /ery unusual .or a simple, sta3le molecule7 But
the oygen molecule is indeed paramagnetic and the simple and clear 6ay in 6hich this
result is o3tained in the C" description is a /ery strong point in .a/our o. the applica3ility
that theory7 A count o. 3onding electron pairs minus anti3onding electron pairs (the t6o
electrons in the t6o (

C"s each contri3ute hal. a 3ond+ sho6s that the oygen molecule
has an ecess o. t6o 3onds o/er anti3onds in agreement 6ith the usual .ormulation o.
the molecule as "
=
"7
*1%' HETER2NUC5EAR 3IAT2MIC M25ECU5ES
When 6e see4 to apply the C" theory to heteronuclear diatomic molecules 6e ha/e
to consider a pro3lem 6hich did not arise in the homonuclear case7 There, there 6as
ne/er any 0uestion o. the proportions o. A"s in/ol/ed in an C" since, 3y symmetry,
each atom had to contri3ute e0ually7 This is not the case i. the atoms are not the same
as, .or eample, in the hydroyl radical, "9, 6hich is o3ser/ed spectroscopically 6hen
hydrogen 3urns in oygen7 At is also .ormed 3y the photolysis o. 6ater at high altitudes
and is important in the chemistry o. troposphere, i7e7 the atmosphere 3elo6 #0 4m7 The
#s A" o. the hydrogen atom is a3le to .orm a 3onding o/erlap 6ith 3oth the 2s and the
2p
K
A"s o. the oygen atom (K is the internuclear ais+ and 6e may .ormulate C" 6a/e
.unctions such as1
G
=
C
#
$
9#s
+
C
2
$
"2s
+
C
,
$
"2p
K
!?.#,.#"
But 6e do not 4no6 the relati/e magnitudes o. the three coe.Lcients, C
#
, C
2
and C
,
, i7e7 6e do not 4no6 to 6hat degree the t6o atoms contri3ute their A"s to the C"7 The
method 3y 6hich the /alues o. C
#
, C
2
and C
,
could 3e .ound 6as 4no6n e/en 3e.ore the
ad/ent o. 0uantum mechanics since similar types o. pro3lem occur in classical mechanics7
But apart .rom a .e6 small molecules and the special case o. the con@ugated hydrocar3ons
(see Section #27#+, it 6as scarcely possi3le to sol/e the necessary e0uations 3e.ore the
ad/ent o. the digital computer in the #$50s7
;o6adays, numerous computer programs .or sol/ing the pro3lem at di..erent le/els o.
approimation are a/aila3le7 The method employed is to use the /ariation method to Lnd
the 3est /alues o. the C
i
s 3y setting up the secular e0uations in the manner descri3ed in
detail in Appendi 27 An this particular case the measurea3le property, P , o. Appendi 2
is the energy, E, and the associated operator is the 9amiltonian, 9

7
An energy2le/el diagram .or "I9 calculated 6ith such a program .or the eperimen2
tally o3ser/ed "I9 3ond length o. $-70 pm is sho6n in Digure ?7#07 The positi/e lo3e
o. the oygen 2p
K
or3ital is directed to6ards the hydrogen atom7 "n the right o. the
diagram the #s A" o. hydrogen is sho6n at an energy o. #,7?0 e87 "n the le.t o. the
diagram the 2s and 2p A"s o. the oygen atom are plotted at ,27,0 e8 and #*7%0 e8
respecti/ely7 The oygen #s A" is not in/ol/ed in the 3onding and does not .eature in
the diagram7 An the centre o. the Lgure the calculated energy le/els o. "I9 are sho6n at
,,7,$ e8, #57%5 e8, #*7%0 e8 (dou3ly degenerate+ and +?7?2 e87 The dots indi2
cate the Llling o. the a/aila3le C"s 6ith electrons7 "n the .ar right o. the Lgure the
coe.Lcients o. the A"s, i7e7 C
#
, C
2
and C
,
, .or each ' C" are sho6n7 They tell us ho6
each A" contri3utes to each C" and the signs also sho6 the 3onding or anti3onding
nature o. the C"7 Ammediately 3eneath each coe.Lcient its s0uare is entered 3ecause it
is the s0uare o. the 6a/e .unction 6hich gi/es the electron density and the second ro6
#52 The Co/alent Chemical Bond
)#0
0
'nergy (e8+
"I9 :adical
s
3
"2pK "2s 9#s
07?$ 07-0 #720
07*- 07*$ #7**
I#0
I20
"2p
9#s
p
s
2
07%- 0720 072?
07-? 070* 070-
I,0
"2s
070* 07%$ 072#
s
1 0700 07-$ 070*
I*0
I + +
+
6ig;re *1%. A molecular or3ital energy2le/el scheme .or the "9 radical
o. Lgures there.ore re/eals ho6 the electrons are distri3uted in that particular C"P i. it
contains any7
Let us Lrst consider the C" o. lo6est energyP '
#
, E
=
,,.,$ e87 The ma@or con2
tri3utor 6ith a coe.Lcient o. +07%%$ is the oygen 2s A" and hydrogen #s also plays a
part 6ith a coe.Lcient o.
+
072#27 The contri3ution o. oygen 2p
K
is too small to concern
us7 ;ote that the or3ital is 3onding, 3ecause the t6o A" contri3utors o/erlap in phase,
and o. ' type7 We place t6o o. our se/en electrons in this C"7
The C" net in energy ('
2
, E
=
#5.%5 e8+ in/ol/es the same three A"s 3ut the
oygen 2p
K
no6 plays 3y .ar the most important role7 ;ote that the oygen 2s2hydrogen
#s o/erlap is anti3onding 6hile the oygen 2p
K
2hydrogen #s o/erlap is 3onding7 The last
is 3y .ar the greater and dominates so that the C" is 3onding in total7 But it is important
to o3ser/e that, 6here many A"s are in/ol/ed, 3oth 3onding and anti3onding interactions
can 3e .ound 6ithin the same C"7
The net t6o C"s, the degenerate pair o. ( symmetry at E = #*.%0 e8, are non2
3onding C"s7 The ( 2type oygen 2p

and oygen 2p
y
A"s ha/e Kero o/erlap 6ith the
' 2type hydrogen #s A" and there is no interaction 3et6een them7 Conse0uently these
t6o oygen 2p A"s are .ound in the molecule 6ith an unchanged energy o. #*7%0 e87
Their A" coe.Lcients are each #707 Since se/en electrons are a/aila3le to Lll the C"s o.
"I9 (the oygen #s electrons 3eing omitted .rom the diagram+, the last three electrons
must 3e placed in these t6o or3itals, o. 6hich one 6ill 3e only hal.2.ull7 The unpaired
electron ma4es the "I9 radical paramagnetic and /ery reacti/e7
The highest C" ('
,
+ is /ery high in energy (E
= +
?.?2 e8+ and strongly anti3onding
in all its o/erlaps7 A. electrons Lnd their 6ay into this C", 3y a3sor3ing light .or eample,
the molecule 3ecomes e/en more reacti/e7
An order to indicate, in a simple manner, the 6ay in 6hich the /arious A"s contri3ute
to the C"s lines connecting A"s and C"s are .re0uently dra6n, as in Digure ?7#07
"ccasionally lines o. di..ering thic4ness or dotted lines are used to indicate greater or
smaller A" contri3utions7
*1%( CHARE 3ISTRI8UTI2N
A .urther piece o. interesting in.ormation can 3e o3tained .rom the results o. an C"
calculation7 Drom the atomic or3ital coe.Lcients .or each occupied C" and the calcu2
lated o/erlap integrals the distri3ution o. the electrons throughout the molecule may 3e
calculated7 An the present eample o. the "I9 radical it is .ound that the se/en /alence
electrons are distri3uted such that ?7*% o. them are on the oygen atom and 0752 on the
hydrogen7
]
Thus, the hydrogen carries a partial positi/e charge o. approimately +e,2
and the oygen a partial negati/e charge o. e,2, 6here e is the charge on the proton7
This type o. analysis o. the distri3ution o. the electrons 6ithin the molecule is usually
termed Culli4en population analysis, a.ter :7S7 Culli4en 6ho Lrst introduced the idea7
*1%) HY8RI3ISATI2N AN3 RES2NANCE
The .act that a description o. the electronic structure o. a molecule is usually easier in
terms o. the C" rather than the 8B model stems .rom the .act that in the .ormer 6e
lea/e all consideration o. the electrons and their spins until the Lnal step I the Llling o.
the C"s 6ith electrons7 An the 8B model, on the other hand, 6e .orm our trial 6a/e
.unction .rom atoms complete 6ith their electrons, 6hich ha/e to 3e unpaired in
their atomic or3itals so that they can pair 6ith unpaired electrons on the other reacting
atom(s+7 An Sections ?7#5 and ?7#? 6e introduce the concepts o. hy*ridisation and
resonance, 6hich arose .rom this re0uirement .or complete atoms 6ith unpaired
electrons and .orm an important part o. the 8B model7
*1%)1% H0?ri/isation: !a;ling %-'%
Linus Carl !auling (#$0# I #$$*+ 6as the greatest chemist o. the 20th century7 <uring
a long career he made momentous contri3utions to chemistry and 6as also acti/e in 6orld
a..airs7 9e 6as a6arded the ;o3el !riKe .or Chemistry in #$5* and the ;o3el !eace !riKe
in #$?,7 The concept o. hy3ridisation, 6hich he put .or6ard in #$,#, is more important
in the 8B theory than in the C", as 6e shall see in Section ?7#5727 But 6e can readily
appreciate the need .or such an idea, e/en 6ithin the C" theory7 The construction o.
C"s .or 9I9 is /ery simple since 6e must al6ays ha/e e0ual contri3utions .rom the
t6o hydrogen atoms and there are only t6o hydrogen #s A"s to 3e considered7 When
6e see4 to .orm C"s .or molecules 6hich ha/e 2s and 2p /alence A"s many ne6
pro3lems present themsel/es, e/en 6hen @ust t6o identical atoms are to 3e com3ined, as
6e ha/e seen in Section ?7#27 A. the atoms to 3e com3ined are di..erent, and especially
]
This statement means that each electron spends ?7*%H- or $, Y o. its time in the /icinity o. the oygen atom and 0752H-
or - Y o. its time in the /icinty o. the hydrogen atom7
F

o
r

R

a

i
s

(
a
0
+
i. there are more than t6o, the pro3lem o. choosing suita3le com3inations o. A"s can
3e /ery complicated indeed7 Consider the three C"s o. "I97 T6o A"s o. oygen, the
2s and the 2p
K
, are al6ays in/ol/ed, al3eit sometimes in a rather une0ual measure7 But
they 3oth play a /ery signiLcant role in the C" o. highest energy 6ith /ery nearly
e0ual contri3utions .rom each7 This o3ser/ation leads to a potential simpliLcation in the
construction o. C"s7 :ather than consider the oygen 2s and oygen 2p
K
A"s separately,
6e Lrst ma4e com3inations o. them o. the .orms1

#
and
$
+
=
$

=
2
!$
2s
+
$
2p
K
" !?.#5.#a"

#
2
!$
2s

$
2p
K
" !?.#5.#3"
These or3itals are called hy3rid atomic or3itals and a contour diagram o. $
+
is sho6n
in Digure ?7##7 $

has eactly the same .orm 3ut the larger lo3e is directed along K7
'ach hy3rid or3ital is much enhanced in one direction and is there.ore particularly suited
to 3onding interaction 6ith the A"s o. a second atom lying in that direction7 An this /ie6,
the lo6est ' C" (
'
+ 6ill 3e the com3ination o. $
+
6ith hydrogen #s, i7e71

# #

#
'
=
2
!$
+
+
$
#s
"
=
2
!$
2s
+
$
2p
K
"
+
2
$
#s
(?7#572a+
There 6ill also 3e a strong anti3onding interaction 3et6een $
+
and 9#s corresponding
to the 6a/e .unction
'

1
# #

#
'

=
2
!$
+

$
#s
"
=
2
!$
2s
+
$
2p
K
"

2
$
#s
(?7#5723+
2
#
0720
0
07,0
0750
0720
07,0 07#0
07#0
07*0
#
0
2
"ygen sp hy3rid
# 0 # 2
N ais (a
0
+
6ig;re *1%% An sp hy3rid or3ital .or oygen
The other hy3rid !$

" points a6ay .rom the hydrogen atom and 6ill there.ore play
little part in the 3onding to that atom, i7e7 it 6ill 3e a non23onding or3ital7 Thus, 6e
ha/e simpliLed our thoughts a3out the 3onding in "I9 3y reducing the pro3lem to
one o. the interaction o. a single hy3rid or3ital ($
+
+ rather than t6o atomic or3itals,
$
2s
and $
2p

7 An energy le/el scheme .or "I9 constructed 6ith hy3rid oygen A"s is
sho6n in Digure ?7#27 This scheme is purely 0ualitati/e and no attempt has 3een made
to o3tain numerical /alues .or the energy le/els, .or reasons 6hich 6ill 3e made clear in
Section ?7#5757
The correspondence 3et6een the calculated C" scheme in Digure ?7#0 and the one
constructed 6ith hy3rid A"s is not particularly good in this case, since the assumption
that the 2s and 2p
K
A"s o. the oygen atom contri3ute e0ually to the t6o hy3rids is
a /ery poor one .or the t6o lo6er C"s7 Close inspection o. the A" coe.Lcients in
Digure ?7#0, or their s0uares, sho6s that the oygen atom contri3ution to the 3onding
C" ('
#
+ is entirely oygen 2s 6hile the contri3ution to the non23onding C" ('
2
+ is
almost eclusi/ely oygen 2p7 This illustrates a 6ea4ness o. the hy3rid or3ital approach
to chemical 3onding, 3ut it has the great ad/antage that 6e can construct an energy2
le/el scheme, 0uite literally, Qon the *ac; of an envelo%e G7 Durthermore, the use o. hy3rid
A"s leads to /ery speciLc predictions concerning molecular geometry, as 6e shall see
in more detail in Section ?7#57,7 Dor the moment 6e note that the .ormation o. a hy3rid
A" usually leads to an A" that points strongly in a particular direction in space and
is there.ore /ery 6ell suited to o/erlap 6ith the A"s o. a second atom 6hich lies in
that direction, 6hile the o/erlap 6ith the A"s o. an atom in any other position is much
diminished7
c("2s + "2p+ c9#s
"ygen hy3rid 9#s
anti3onding C"
c("2s "2p+
"ygen hy3rid
non23onding C"
"ygen hy3rid 9#s
3onding C"
c("2s + "2p+ + c9#s
"r3ital phases1 positi/e negati/e
6ig;re *1%& Colecular or3ital energy2le/el scheme .or the ' C"s o. "I9 using sp hy3rid oygen
or3itals
*1%)1& H0?ri/isation an/ t$e Aalen#e ?on/ t$eor0
:ecall the essential di..erence 3et6een the 6ays in 6hich the simplest trial 6a/e .unction
.or the hydrogen molecule 6as constructed using the C" and the 8B theories7 An the C"
theory, the .orm o. a molecular or3ital 6as Lrst determined (as the sum o. t6o hydrogen
#s A"s+ and the t6o electrons 6ere then placed in that C" 6ith their spins paired7 An the
8B theory, ho6e/er, the t6o hydrogen atoms, complete 6ith their electrons, 6ere 3rought
together in such a 6ay that their spins paired7 The hydrogen molecule is eceptional in
that a .air approimation to the molecular 6a/e .unction can 3e o3tained, 3y either the
C" or the 8B method, using only t6o A"s7 An almost all other molecules more than t6o
A"s are in/ol/ed in the 3onding o. t6o or more atoms7 At is 0uite easy to etend the C"
theory to em3race a large num3er o. A"s, 3ut this is not true o. the 8B theory 6here
6e need to Lnd a single electron in an A" on one com3ining atom 6hich can 3e paired
6ith another unpaired electron occupying an A" on another com3ining atom7 (We re0uire
a singly occupied A" 3ecause 6e must pair electrons to .orm 3onds7+ Durthermore, 6e
normally re0uire a hy3rid or3ital on at least one o. the com3ining atoms 3ecause 6e need
to direct the or3ital /ery speciLcally to6ards the other atom i. 6e are to .orm a strong
3ond7 But in atoms the electrons, .ollo6ing the au.3au (3uilding2up+ and !auli principles,
occupy the or3itals in pairs 6ith opposed spins7 Thus, the Lrst step in a 8B description
o. the chemical 3onding in a polyatomic molecule is the .ormulation o. a set o. singly
occupied hy3rid A"s .or the atoms in/ol/ed7 The classic and most important eample o.
this is the description o. the 3onding 3et6een car3on and hydrogen and 3et6een car3on
and car3on in the hydrocar3ons7
*1%)1' H0?ri/isation o" #ar?on A2s
An Section ?7#57# 6e noted 3rieOy that the .ormation o. hy3rid A"s has many implications
.or molecular geometry and it is use.ul, there.ore, to re/ie6 /ery 3rieOy the ma@or .eatures
o. the geometry o. the hydrocar3ons, 6hich any theory should reOect, 3e.ore 6e proceed
to discuss the A" hy3ridisation in these compounds7
Type #1 The car3on atom is 3onded to .our other atoms arranged at the corners o. a
tetrahedron 6ith the car3on atom at the centre7 The 3ond angles at the car3on
atom are /ery close to the tetrahedral angle o. #0$75

7 'amples are methane


and the higher saturated hydrocar3ons7
Type 21 The car3on atom is 3onded to three other atoms and all .our atoms lie in a plane
6ith 3ond angles at the car3on atom o. approimately #20

7 'amples are ethene


and the aromatic hydrocar3ons7
Type ,1 The car3on atom is 3onded to t6o other atoms and the 3ond angle at the car3on
atom is #%0

7 'thyne is the 3est eample o. this type o. 3onding7


The car3on atom in its state o. lo6est electronic energy has the conLguration
(#s+
2
(2s+
2
(2p+
2
6here, in accordance 6ith 9undGs rule, the t6o 2p electrons occupy
di..erent 2p A"s 6ith parallel spins7 The car3on atom has only t6o unpaired electrons
and 6e might there.ore epect that it 6ould .orm @ust t6o 3onds7 Durthermore, since any
t6o p A"s are orientated at right2angles to each other 6e might epect that these t6o
3onds 6ould enclose an angle at the car3on atom o. approimately $0

7 These predictions
are totally at /ariance 6ith the ma@or .eatures o. hydrocar3on structure outlined a3o/e7
A. 6e are to .orm .our 3onds 6e must, in a 8B description, Lrst generate .our unpaired
electrons7 There is one o3/ious 6ay o. doing this and that is to promote one o. the 2s
electrons to the /acant 2p A"7 This promotion re0uires energy7 But i. it leads to more and
stronger 3onds then the energy o. the molecule Lnally .ormed 6ill 3e that much lo6er,
i7e7 the molecule 6ill 3e more sta3le, and the in/estment o. energy 6ill ha/e 3een 6orth
6hile7 The eperimental o3ser/ation o. compounds o. Type #, and theoretical calculations
pro/e that the o/erall energetics o. the process are .a/oura3le7
But the promotion o. a 2s electron to a 2p A" is not o. itsel. su.Lcient to eplain the
tetrahedral geometry o. Type # compounds7 An .act, in the case o. methane .or eample,
the car3on atom conLguration (#s+
2
(2s+
#
(2p

+
#
(2p
y
+
#
(2p
K
+
#
might 3e epected to
produce three identical CI9 3onds directed along the , y and K aes and one di..erent
3ond 6ith no particular directional characteristics7 But, eperiment sho6s that
methane has .our
identical CI9 3onds 6ith 9ICI9 angles o. #0$75

7 Clearly, something more is re0uired7


Since the geometry o. methane is tetrahedral, it is clear that the strongest CI9 3onds
are .ormed .rom hy3rids 6ith enhanced electron densities along .our tetrahedral directions7
Digure ?7#, sho6s a cu3e in 6hich the three cartesian aes pass through the centre point
o. the .aces and 6e place a car3on atom at the centre o. the cu3e, 6hich is also the origin
o. the coordinate system7 A. 6e no6 place .our hydrogen atoms at alternate corners o.
the cu3e 6e ha/e a model o. the methane molecule7 The hydrogen atom # (9
#
+ at
+
x,
+y, +B, .or eample, is identically placed 6ith respect to the three car3on 2p or3itals
and a com3ination o. all three 2p A"s in e0ual proportions (2p

+
2p
y
+
2p
K
+ must, 3y
symmetry, produce a hy3rid or3ital directed along the line CI9
#
7 A hy3rid A" directed
to6ards 92 can 3e .ormed 3y the com3ination 2p

2p
y
+ 2p
K
7 And similarly .or
9, and 9*7 Since the 2s A" is spherically symmetrical it has no inOuence upon the
directional properties o. the hy3rid A"s, 3ut 6e must use it since 6e need .our hy3rid
A"s in total and these can only 3e constructed .rom an e0ual num3er o. unhy3ridised
A"s7 We there.ore ha/e to .ulLl the .ollo6ing re0uirements .or our hy3rid A"s1
The .our hy3rid A"s must QconsumeG all the .our 2s and 2p A"s o. the car3on atomP
no more and no less7
N
+ +
2
+ +
#
+
+
C R
+
,
+

F
*
(3+ (c+
(a+
6ig;re *1%' The methane molecule 6ith the .our hydrogen atoms (# *+ arranged at the corners
o. a cu3e centred at the car3on atom7
0
0705
07#0
0720
0720
07,0
07,0
07#0
0705
Car3on sp
,
hy3rid
2
2
2
2
F

o
r

R

(
a
0
+

The resulting hy3rid A"s must point to the corners o. a tetrahedron, i7e7 they must
contain the 2p A"s 6ith the appropriate signs as indicated .or 9# and 92 a3o/e7
Apart .rom their direction in space, all the hy3rid A"s must 3e eactly the same, i7e7
they must each contain the same proportions o. 2s and 2p A"s7
'ach hy3rid A" must 3e normalised to one7
The a3o/e re0uirements are satisLed 3y the hy3rids1
G
#
=
#
{$
2s
+ $
2p
G
2
=
#
{$
2s
$
2p
G
,
=
#
{$
2s
$
2p
+ $
2p
y
$
2p
y
+ $
2p
y
+ $
2pK
} (?7#57,a+
+ $
2p
K
} (?7#57,3+
$
2p
K
} (?7#57,c+
G
*
=
#
{$
2s
+ $
2p
$
2py
$
2p
K
} (?7#57,d+
9y3rid A"s o. this .orm are usually 4no6n as sp
,
hy3rids since they are composed o.
one 0uarter s and three 0uarters p A"s7 The proo. that they are orthogonal and normalised
is gi/en in Bo ?72 and a contour plot is sho6n in Digure ?7#*(a+7 The hy3rid A"s are
clearly highly directional and in a 8B calculation o. the methane molecule one electron
6ould 3e placed in each hy3rid A" and com3ined 6ith the singly occupied #s A" o.
the hydrogen atom to 6hich it is directed7 The interaction 6ith hydrogens at the other
corners o. the tetrahedron 6ould 3e neglected as a Lrst approimation7
The 3onding in hydrocar3ons o. Type 2 geometry can 3e interpreted in terms o. hy3ridi2
sation in a similar 6ay7 Consider the ethene molecule (Digure ?7#5+7 All si atoms lie in
the y2plane so the car3on 2p
K
A" plays a role di..erent .rom that o. the 2p

and 2p
y
7
,
2
#
0
#
2
6ig;re *1%(
,
2 # 0 # 2 ,
N (a
0
+
(a+
0705
0
07#0
0705
0720
07,0
0720
07,0
07#0
Car3on sp
2
hy3rid
07#0
0
0720
0705
0720
07,0
0705
07,0
07#0
Car3on sp hy3rid
F

o
r

R

(
a
0
+
F

o
r

R

(
a
0
+
,
2
#
0
#
2
,
2 # 0 # 2 ,
N (a
0
+
(3+
,
2
#
0
#
2
,
2 # 0 # 2 ,
N (a
0
+
(c+
6ig;re *1%( Car3on sp
,
, sp
2
and sp hy3rid or3itals
R
9
9
C C F
9
9
6ig;re *1%) 'thene
The car3on 2s, 2p

and 2p
y
are com3ined to .orm hy3rid A"s according to the .ollo6ing
e0uations1

G
#
=
!#,

G
2
=
!#,

?"{
?"{

2$
2s

$
2p

+

2$
2s

$
2p

,$
2p
y
}
(?7#57*a+

,$
2p
y
}
(?7#57*3+
G
,
=
!#, ,"
{
$
2s
+
2$
2p

}
(?7#57*c+
9y3rids o. this .orm are called sp
2
hy3rids 3ecause they are composed o. one third s
and t6o thirds p A"s7 They are directed to6ards the corners o. an e0uilateral triangle and
are there.ore ideally suited .or o/erlap and electron pairing 6ith atoms lying in a plane
and su3tending 3ond angles o. #20

7 They are also orthogonal and normalised7 The 2p


K
A" o. the car3on atom is not in/ol/ed in the hy3rids and there.ore remains a/aila3le .or
3onding 6ith 2p
K
A"s on ad@acent car3on atoms7 Whereas the o/erlap o. the sp
2
hy3rid
A"s gi/es rise to ' 3onding, the o/erlap o. the 2p
K
A"s on ad@acent car3on atoms results
in ( 3onding and the CIC 3ond in ethene is a dou3le 3ond 6ith ' and ( contri3utions7
The most important eample o. this type o. 3onding is .ound in the aromatic hydrocar3ons
o. 6hich 3enKene is the simplest representati/e7 An ( 3onding the electrons are not tightly
conLned in the internuclear region as they are in ' 3onding7 The nature o. ( 3onding
is such that the electrons in/ol/ed in it lie a3o/e and 3elo6 the plane o. the molecule
and are a3le to mo/e o/er all the car3on atoms .orming the molecule7 These delocalised
electrons are responsi3le .or the many properties o. the aromatic hydrocar3ons 6hich
distinguish them .rom the sp
,
23onded, saturated hydrocar3ons7 Dor eample, almost all
organic dyes are 3ased upon aromatic hydrocar3ons and the .act that they a3sor3 light in
the /isi3le region o. the spectrum, rather than at higher energy in the ultra2/iolet, is due
to the presence o. ( 2electron C"s7
'thyne (Digure ?7#?+ is a typical eample o. hydrocar3ons o. Type , in 6hich the
geometry at the car3on atom is linear7 The simple sp hy3rid A"s1

#
and
G
#
=
G
2
=
2
{
$
2s

$
2p

}
!?.#5.5a"

#
2
{
$
2s
+
$
2p

}
!?.#5.53"
produce 3onds to the hydrogen and car3on atoms 6ith an 9ICIC 3ond angle o. #%0

7
The remaining, unhy3ridised 2p
y
and 2p
K
A"s on the car3on atoms .orm t6o ( 3onds
gi/ing a total o. three 3onds in accord 6ith our usual .ormulation o. the CC triple 3ond
in ethyne7 Since they are .ormed .rom 2p A"s at $0

, the t6o ( 3onds are also at right


angles to each other7 As in the case o. Type 2 compounds, this ( 3onding pro/ides a 6ay
in 6hich the electrons in/ol/ed can 3e delocalised o/er the 6hole car3on2atom system i.
the triple 3onded car3ons are lin4ed to others as in the polyethynes7 Some /alues o. CI9
and CIC o/erlap integrals calculated 6ith Slater2type A"s (Bo ?7,+ and hy3rid A"s are
gi/en in Ta3les ?7, and ?7*7
6ig;re *1%* 'thyne
9 C C 9
'
(
Ta?le *1' Car3on I hydrogen atomic or3ital
o/er2 lap .or Slater2type car3on 2p and 2s and A"s
a
6ith
O

=
,.25 and a hydrogen #s A" 6ith O

=
#.2
r!CI9" = #0$.0 pm r!CI9" = #0$.0 pm
9#s|C2s = 0.5%5# 9#s|Csp
,
= 0.-?$?
9#s|C2p
K
= 0.550$ 9#s|Csp
2
= 0.-%-?
9#s|Csp = 0.%0,,
a
Bo ?7, ;ote ho6 the o/erlap o. the hydrogen #s 6ith
the car3on hy3rid A"s eceeds the o/erlap 6ith unhy2
3ridised car3on A"s7
Ta?le *1( Car3on I car3on atomic or3ital o/er2
lap .or Slater2type A"s
a
6ith O

= ,.25
Bond CIC C=C CC
rHpm #5*7, #,57, #207%
*
2s|2s 07,,$# 07*,0# 0750-0
2p|2p
07,2%% 07,2?? 072$,#
c
2p|2p
07#$0$ 072?*2 07,,,*
d
sp
,
|sp
,
07?*?? 07-2,? 07-5,$
sp
2
|sp
2
07?-5* 07-?5# 07%0-%
sp|sp 07?$-$ 07%0?$ 07%-0*
a
Bo ?7,7
*
The 3ond lengths correspond to typical single, dou3le
and triple car3on I car3on 3onds7
' c
The

2p
|
2p

o/erlap decreases as the 3ond length
decreases due to the o/erlap o. positi/e and negati/e
portions o. the 2p A"s7
(
d
The 2p|2p
decreases7
o/erlap increases as the 3ond length
*1%)1( T$e #$oi#e o" $0?ri/ or?itals
The reader may regard the preceding discussion o. hy3ridisation in hydrocar3ons as a
rationalisation o. the eperimentally o3ser/ed geometries, rather than a description o. a
procedure 3y means o. 6hich the eperimental energies and geometries may 3e calculated7
9o6e/er, to ta4e methane as our eample, the choice o. tetrahedral hy3rids is simply a
rational Lrst step, gi/en that a set o. singly occupied or3itals on the car3on atom is an
important simpliLcation in the application o. the 8B theory to methane7 A. 6e choose to
use the 2s and three 2p A"s o. car3on as our starting point, 6e 6ould o3tain eactly the
same result in the end, and it 6ould 3e possi3le to epress the molecular 6a/e .unction
o3tained in eactly the same .orm as that determined .rom an initial assumption o. sp
,
hy3rids, 3ut the calculation 6ould 3e considera3ly more complicated7 The Lnal results,
ground state energy and 6a/e .unction, are not determined 3y the starting point7
An interesting and detailed analysis o. this pro3lem, .rom a /ie62point 6hich appears to
ha/e 3een ta4en 3y .e6 other authors, has 3een gi/en 3y J7 W7 Linnett7
-%
Linnett eplored
the conse0uences o. the !auli elusion principle on the /alence electron distri3ution in
atoms7 An outline o. his approach is gi/en in Bo ?7*7 The .act that electrons o. the same
spin cannot occupy the same region o. space 3ecause o. the !auli principle, together 6ith
their mutual electrostatic repulsion, means that electrons o. di..erent spins tend to 4eep
together 6hile those o. the same spin 4eep apart7 Thus, .or neon, the electron distri3ution
o. highest pro3a3ility, as .ar as spin correlation e..ects are concerned, is an outer shell
consisting o. .our electron pairs at the corners o. a regular tetrahedron7
This 6ould also 3e true o. the C
*

ion, i. it eisted7 Thus, 6hen C
*

3inds to .our
protons the strongest 3onds 6ill 3e .ormed i. the protons are arranged at the corners o. a
regular tetrahedron7 The .ormation o. electron2pair 3onds rein.orces the pairing tendency
o. electrons ha/ing opposed spins7 An this /ie6, the choice o. .our tetrahedral sp
,
hy3rids
.or car3on 6ould 3e a natural choice, e/en i. 6e did not 4no6 the geometry o. methane7
These ideas do not appear to ha/e 3een 6idely eplored and this may 3e 3ecause a theory
o. molecular geometry, apparently 3ased purely upon electron repulsion, 6hich leads to
essentially the same conclusions in a manner 6hich is easier to apply, has .ound 6ider
acceptance7 This approach to molecular geometry is descri3ed in detail in Section ?7#-,
3ut it should 3e noted here that the concepts outlined immediately a3o/e pro/ide the
theoretical .oundation o. the simpler method (Bo ?7*+7
*1%)1) T$e properties o" $0?ri/9or?ital ?on/s
The .act that the o3/ious choice o. hy3rid or3itals reOects so precisely the salient .eatures
o. the molecular geometry o. hydrocar3ons and emphasises the t6o2electron nature o. each
identical CI9 3ond are the strong points o. the 8B theory and go a long 6ay to eplain
6hy concepts deri/ed .rom it, resonance (see Section ?7#?+ .or eample, are so pre/alent
in organic chemistry7 Andeed, these points are so appealing to the chemist see4ing a
0uantum2mechanically 3ased understanding o. molecular structure that the hy3rid or3itals
themsel/es can easily 3e ele/ated to a signiLcance a3o/e their true status7 This pro3lem is
especially clear 6hen 6e consider energiesP and 6e again ta4e methane as our eample7
Because all .our CI9 3onds are 4no6n eperimentally to 3e identical, and this .act
is echoed in the 8B description o. the molecule using .our sp
,
hy3rids, it is tempting to
conclude that there is a .our2.old degeneracy in the electronic energy le/els o. methane7
But i. 6e measure the energies o. the methane /alence electrons using photo2electron
spectroscopy, 6e Lnd a set o. three degenerate energy le/els at a3out #, e8 and a
single energy le/el at a3out 2, e87 Calculations sho6 that the triply degenerate le/els
arise .rom the 3onding o. the .our hydrogen #s A"s to the car3on 2p A"s and the single
le/el .rom the 3onding 3et6een the hydrogen #s or3itals and the car3on 2s A"7 That
this should 3e so is immediately conLrmed 3y a study o. Digure ?7#,, 6hich sho6s that,
3ecause o. the high cu3ic symmetry, each o. the three car3on 2p A"s has eactly the same
3onding interaction 6ith the appropriate phase com3ination o. the .our hydrogen #s A"s
6hile that o. the car3on 2s A" is clearly di..erent7 (Digures ?7#,(3+ and ?7#,(c+ sho6 the
or3ital phases .or 3onding o/erlap 3et6een the .our hydrogen #s A"s and the car3on 2s
and car3on 2p
K
A"s respecti/ely7 Dor clarity the A"s are not sho6n o/erlapping7+ The
price that 6e pay .or the simple description o. 3onds and their orientation pro/ided 3y
hy3ridisation is the loss o. in.ormation on energy 6hich use o. the unhy3ridised car3on
2s and 2p A"s ma4es o3/ious7 9y3rid or3itals, unli4e atomic and molecular or3itals,
are not eigen.unctions o. an energy operator and it is important to grasp this .act7 But
0uantum2mechanical 6a/e .unctions do not ha/e to 3e eigen.unctions o. some operator
in order to 3e o. /alue to us7
Colecular Geometry #?,
I
I
" " "
C C C
" " " " " "
I I I I
(a+
(3+
6ig;re *1%+ :esonance structures o. 3enKene (a+ and the car3onate anion (3+
*1%* RES2NANCE AN3 THE VA5ENCE 82N3 THE2RY
The 8B theory is also the origin o. and pro/ides the theoretical @ustiLcation .or the con2
cept o. resonance 6hich is /ery 6idely used in chemistryP in spite o. 3eing declared
incompati3le 6ith dialectical materialism in Stalinist :ussia7 Consider the .amiliar struc2
tural .ormulae .or 3enKene (Digure ?7#-(a++7 The three lines that ha/e di..erent positions in
the t6o structures represent the di..erent possi3le pairings o. the electrons in the car3on
2p
K
A"s7 Both o. these pairing schemes are re0uired to descri3e the 3onding in 3en2
Kene in a 8B calculation 6here the electrons, 6ith speciLed spin .unctions, are assigned
to A"s in the Lrst step o. the calculation7 The t6o structures are 4no6n as resonance
.orms o. 3enKene and 6e must 3e care.ul to recognise that they ha/e no independent
eistence7 'ach contri3utes e0ually to our 8B description (6a/e .unction+ o. the 3onding
in 3enKene7 Both are essential, 3e it in a representation o. the 3onding on paper or in
the mathematical .ormulation o. the 8B 6a/e .unction7 (The .ormulation o. 3enKene as
a ring inside a regular heagon is more a4in to an C" representation o. the electronic
structure7+ :esonance structures occur etremely .re0uently in discussions o. molecular
electronic structure7 An the case o. the car3onate anion (Digure ?7#-(3++, .or eample, three
structures are re0uired to epress the .act that all CI" 3onds are eactly the same7 This
cannot 3e sho6n 6ith one classical /alence (electron pairing+ structure7
*1%+ M25ECU5AR E2METRY
Any sel.2respecting theory o. molecular electronic structure must ha/e the a3ility to
predict molecular geometry7 A. calculations o. su.Lcient accuracy can 3e per.ormed, then
it is only necessary to repeat the calculation o. the total electronic energy o. the molecule
.or a /ariety o. geometries and to determine the geometry 6hich gi/es the lo6est (most
negati/e+ energy7 This 6ill 3e the e0uili3rium eperimental geometry o. the molecule7
But there are aspects o. this apparently straight.or6ard approach 6hich are unsatis.actory
i. 6e see4 a 6idely applica3le solution to the pro3lem7
The most important di.Lculty arises .rom the re0uired accuracy o. the calculation7 The
change in the total energy o. a molecule 6hich results .rom a small change o. 3ond angle
6ill normally 3e less than 07# Y o. the total energy7 Clearly, a /ery accurate and there.ore
tedious calculation is re0uired to achie/e this le/el o. accuracy .or a small molecule, and
it may 6ell 3e impossi3le .or a large molecule7 The practising chemist needs a theory
that can 3e applied more easily, and here 6e again recall the maim o. Wigner and SeitK
(Section ?72+7 What 6e re0uire is a pictorial /ie6 o. a molecule .rom 6hich 6e can dra6
conclusions a3out its geometry and particularly its 3ond angles7 The 8B theory 6ith its
emphasis upon the o/erlapping and interaction o. t6o singly occupied A"s, one .rom
each o. the atoms .orming the 3ond, is 3etter suited to this purpose than is the C" theory7
#?* The Co/alent Chemical Bond
Ta?le *1) Bond angles in simple hydrides
Colecule
F9
,
9IFI9 angle
(degrees+
FI9
(pm+
Colecule
F9
2
9IFI9 angle
(degrees+
FI9
(pm+
F F
; #0-7% #0#7- " #0*75 $57-
! $,7? #*#7$ S $27# #,,7?
As $#7% #5#7$ Se $# #*?
S3 $#7, #-07- Te $0 #-07-
Consider the 6ater molecule (9
2
"+7 ;eglecting the #s electrons, the electron conLguration
o. the oygen atom is1 (2s+
2
(2p

+
2
(2p
y
+
#
(2p
K
+
#
7 Dour o. the si /alence electrons
occupy the oygen 2s and one o. the oygen 2p A"s (6e ha/e ar3itrarily chosen the
2p

+ 6ith their spins paired and the remaining t6o electrons occupy the other t6o
oygen 2p A"s 6ith parallel spins and are a/aila3le to .orm 3onds7 Since the t6o singly2
occupied oygen A"s ha/e their maimum electron densities directed along the y2 and K2
aes, the greatest o/erlap and hence the strongest 3ond should 3e .ormed 6hen the t6o
hydrogen atoms
lie on those aes and .orm an 9I"I9 3ond angle o. $0

7 An .act, the eperimentally


determined 3ond angle o. the 6ater molecule is #0*75

7 A. the principal 0uantum num3er


2 is replaced 3y ,, then the argument @ust gi/en also applies to the 9ISI9 3ond angle
in hydrogen sulLde, the eperimental /alue o. 6hich is $27#

7 At should also apply to the


hydrides o. Group #5 (5A+ elements7 Ta3le ?75 gi/es some eamples7 These results are
remar4a3le .or such simple considerations7
*1%+1% T$e Aalen#e9s$ell ele#tron9pair rep;lsion FVSE!RG mo/el
An e/en simpler theory 6hich, in its application, ma4es minimal appeal to the concept
o. atomic or3itals 6as Lrst suggested 3y ;787 Sidg6ic4 and 97C7 !o6ell in #$*0 and
ela3orated 3y :7J7 Gillespie and :7S7 ;yholm in #$5-7 At is 4no6n as the Sidg6ic42!o6ell2
Gillespie2;yholm or as the 8alence Shell 'lectron2!air :epulsion (8S'!:+ model7 The
/alence shell electrons are those in the outermost shell o. the atom and they are the only
electrons that play a signiLcant role in the .ormation o. chemical 3onds7 Sidg6ic4 and
!o6ell, recognising that the /alence shell o. a chemically23onded atom contained 3ond
pairs and lone pairs o. electrons, suggested that the orientation in space o. the electron
pairs, and hence o. the 3onds around a central atom, 6ould 3e that 6hich minimises the
inter2electronic repulsion 3et6een them7 The concept 6hich the 8S'!: theory em3odies,
and 6hich 6as ne6 in #$*0, is the idea that lone pairs, i7e7 electrons in the /alence shell
3ut not in/ol/ed in 3onding, also ha/e a /ery important part to play in the determination
o. molecular geometry7
Sidg6ic4 and !o6ell assumed that the 3ond pairs and lone pairs 6ere o. e0ual impor2
tance, 3ut among many reLnements o. the theory Gillespie and ;yholm proposed that the
electrostatic repulsion 3et6een electron pairs diminishes in the se0uence1 lone pair2lone
pair R 3ond pair2lone pair R 3ond pair23ond pair7 The .ollo6ing interpretation o. the
situation is commonly gi/en7 Since a 3ond pair is dra6n a6ay .rom the central atom
to6ards the atom to 6hich it is 3onded, the region o. electron density associated 6ith
such a pair lies .urther a6ay .rom the central atom than does the corresponding region
Colecular Geometry #?5
o. a lone pair and conse0uently the repulsion eerted 3y it is less7 9o6e/er, recent the2
oretical 6or4 has thro6n dou3t upon this eplanation and it appears that the e..ect is
more su3tle7 But the order gi/en a3o/e certainly appears to apply and it pro/ides a use.ul
guide to molecular geometry7 We must hope that .urther 6or4 6ill clari.y the 3asis o.
this /alua3le idea 6hich is /ery easy to use7
We can illustrate the 8S'!: approach to molecular geometry 3y again considering
the shape o. 6ater7 We .ocus our attention upon the region o. space around the central
oygen atom7 The /alence shell o. oygen, i7e7 the shell 6ith principal 0uantum num3er
e0ual to 2, contri3utes si electrons to this region and each hydrogen contri3utes its single
/alence electron7 There.ore, there are eight electrons, i7e7 .our pairs, o. /alence electrons
surrounding the oygen atom7 A. the .our pairs o. electrons 6ere all eactly the same, their
mutual repulsion 6ould 3e at a minimum i. they 6ere located in .our regions directed
to6ards the corners o. an imaginary tetrahedron centred on the oygen atom7 The 9I"I9
3ond angle 6ould then 3e #0$75

7 But the electron pairs are not all identicalP 6e ha/e


t6o 3ond pairs and t6o lone pairs and the une0ual repulsion 3et6een these pairs 6ill
result in an increase o. the angle 3et6een the t6o lone pairs, 6hich 6e cannot measure,
and a decrease in the 9I"I9 angle in accord 6ith o3ser/ation7 Since the sul.ur atom
also has si /alence electrons (n = ,+ eactly the same reasoning can 3e applied to the
hydrogen sulLde molecule so that 3oth 6ater and hydrogen sulLde are predicted to 3e
3ent 6ith 9IFI9 angles less than the tetrahedral angle (Ta3le ?75+7 An ammonia (;9
,
+,
6ith three 3ond pairs and one lone pair, 6e predict that the lone pair23ond pair repulsions
6ill reduce the 9I;I9 3ond angle 3elo6 the tetrahedral angle, as indeed 6e o3ser/e
(9I;I9 in ammonia
=
#0-.%

+7
A num3er o. e..ects may contri3ute to the larger decrease o. the 9IFI9 angle .rom
#0$75

6hen F is a second2ro6 element7 A. 6e compare 6ater and hydrogen sulLde, the
t6o 3onding electron pairs are .urther apart in hydrogen sulLde than in 6ater 3ecause o.
the greater siKe o. the sul.ur atom and 3ecause the smaller electronegati/ity o. the sul.ur
atom allo6s the electrons to mo/e a6ay to6ards the hydrogen atomsP note the longer
SI9 3ond length in Ta3le ?757 This permits a reduction in the 9ISI9 angle relati/e to
the 9I"I9 angle7 A. 6e reLne our argument 3y introducing the concept o. the sort o.
or3itals 6hich the electron pairs might occupy then, since our starting point is a tetrahedral
arrangement, 6e naturally thin4 o. sp
,
hy3rid or3itals7 An this light 6e might then argue
that the tendency to hy3ridisation o. the s and p or3itals is less in sul.ur than in oygen
so that the SI9 3onds are .ormed 6ith sul.ur ,p A"s gi/ing 9ISI9 angles o. $0

7 This
is e0ui/alent to saying that the promotional energy re0uired to hy3ridise the ,s and ,p
A"s o. sul.ur cannot 3e reco/ered in the .ormation o. t6o SI9 3onds7
Dinally, 6e should repeat the 6arning a3o/e7 Although these eplanations o. the trends
in 3ond angle appear plausi3le 6e are dealing 6ith /ery su3tle e..ects and our /ie6s may
re0uire modiLcation in the light o. .urther research on this su3@ect7 LinnettGs ideas, 6hich
.ocus more attention on electron spin (Section ?7#57* and Bo ?7*+, may play an important
role in a .ull understanding o. the 8S'!: model7
*1%+1& T$e VSE!R mo/el an/ m;ltiple ?on/s
The 8S'!: theory treats multiple 3onds in much the same 6ay as it does single 3onds
regarding the t6o or three electron pairs o. a dou3le or triple 3ond as a single super2pair7
'lectron
pairs
Basic
shape
B!s L!s 'ampl
2 linear 2 0 t6o B!Gs at #%0

P linear BeD
2
, trigonal , 0 three B!Gs at #20

P trigonal BD
,
, d 2 # t6o B!Gs at P#20

P 3ent SnCl
2
a
* tetrahedral * 0 .our B!Gs at #0$75

P tetrahedral C9
*
* , # three B!Gs at P#0$75

P trigonal 3ipyramidal ;9
,
* d 2 2 t6o B!Gs at P#0$75

P 3ent "9
2
5 trigonal 5 0 trigonal 3ypyramid o. B!Gs !Cl
5
5 3ipyramidal * # L! in e0uatorial position SD
*
5 , 2 t6o e0uatorial L!GsP eTd2shaped ClD
,
5 2 , three e0uatorial L!GsP linear FeD
2
? octahedral ? 0 si B!Gs at $0

P octahedral SD
?
? 5 # s0uare pyramid AD
5
? d * 2 t6o aial L!GsP planar FeD
*
? d , , implies a central atom 6ith $ electrons
? d 2 * implies a central atom 6ith #0 electrons
#?? The Co/alent Chemical Bond
As an eample 6e may compare the geometries o. car3on dioide and sul.ur dioide7 An
the case o. car3on dioide (C"
2
+, the car3on atom contri3utes .our /alence electrons and
6e must assume that the oygen atoms each contri3ute t6o since oygen is in/aria3ly
di/alent7 (Spea4ing o. the 3onding in the usual 6ay, 6e 6ould say that the car3on atom
.orms one ' 3ond and one ( 3ond 6ith each oygen atom7+ Thus, the /alence electron
region surrounding the car3on atom contains eight electrons, 6hich 6e group into t6o
super2pairs7 Their mutual repulsion is minimised 3y an "ICI" angle o. #%0

and car3on
dioide is predicted to 3e linear7 An the case o. sul.ur dioide (S"
2
+, 6e ha/e ten electrons,
6hich 6e group into t6o super2pairs (S!s+ plus a lone pair7 The arrangement o. lo6est
energy .or three groups o. electron pairs is 3asically one in 6hich they are disposed at
Ta?le *1* 8S'!: predictions o. molecular shapes and eamples
e
Linear Trigonal Tetrahedral
ABA
=
#%0

ABA
=
#20

ABA
=
#0$.5

A
B A A
A
B A
B
A
A A A
Trigonal23ipyramidal "ctahedral
ABA = $0

P 'B' = #20

ABA = $0

A A
' A
A
A B B
'
A A
A A
a
An the /apor phase, not in the solid state7
Computational <e/elopments #?-
Ta?le *1+ 8S'!: interpretation o. molecular shapes
Colecule 8alence electrons Charge Total electrons ;um3er o. pairs Colecular shape
AB
n
A nB B!s S!s L!s
C9
*
* * 0 % * 0 0 tetrahedral
Z;"
2
\
+
5 * +# % 0 2 0 linear
ZACl
2
\
+
- 2 +# % 2 0 2 3ent
a
Z;"
2
\

5 * # #0 0 2 # 3ent
*
ZACl
2
\

- 2 # #0 2 0 , linear
c
"
,
? * 0 #0 0 2 # 3ent
*
!Cl
5
5 5 0 #0 5 0 0 trigonal 3ipyramidal
Z;"
,
\

5 ? # #2 0 , 0 trigonal
ZC"
,
\
2

* ? 2 #2 0 , 0 trigonal
FeD
*
% * 0 #2 * 0 2 s0uare planar
d
ZCl"
*
\

- % # #? 0 * 0 tetrahedral
ZS"
*
\
2

? % 2 #? 0 * 0 tetrahedral
Z!"
*
\
,

5 % , #? 0 * 0 tetrahedral
a
A tetrahedral disposition o. .our electron pairs 6ith t6o lone pairs7
*
A trigonal disposition o. three electron pairs 6ith one lone pair7
c
The three lone pairs occupy the aial positions o. the trigonal 3ipyramidal array o. L/e electron pairs7
d
The t6o lone pairs occupy the aial positions o. the octahedral array o. si electron pairs7
#20

to each other7 The o3ser/ed "ISI" angle o. ##$75

suggests that the 3ond pair23ond
pair and lone pair23ond pair repulsions are /ery similar in this molecule7 This might 3e
rationalised 3y o3ser/ing that the repulsion due to the 3ond pairs has increased 3ecause
they are no6 superpairs o. .our electrons each7 Be that as it may, there is a /ery positi/e
prediction o. a linear car3on dioide molecule and an angled sul.ur dioide, and this is
the ma@or .eature that 6e ha/e to eplain7 Ta3les ?7? and ?7- summarise the application
o. the 8S'!: model7
*1%, C2M!UTATI2NA5 3EVE52!MENTS
The ad/ent o. digital computers and their e/er2increasing po6er has had an enormous
impact on the calculation o. molecular properties 3y 0uantum2mechanical methods7 At
Lrst, apart .rom special pro3lems such as 9
2
, calculations on molecules o. chemical
interest could only 3e carried out i. all the electron2repulsion integrals and many others
6ere treated as parameters 6hich 6ere not calculated 3ut determined 3y comparison o.
theory and eperiment and inserted into the calculation at the outset7 ;ota3le ad/ances
6ere made 6ith these semi+em%irical C" methods and they are only no6 decreasing in
importance as the a*+initio C" methods, in 6hich all integrals are calculated .rom scratch,
are 3ecoming increasingly .easi3le7 The corresponding de/elopments in 8B theory did
not ta4e place since it pro/ed to 3e much more di.Lcult to implement the 8B theory
computationally, largely on account o. the re0uirement that the electron spins, correctly
paired, 3e introduced at the start o. the calculation rather than at the endP compare the
t6o treatments o. the hydrogen molecule (Sections ?7* to ?7-+7 But nota3le ad/ances in
the 8B theory and coding it 6ere made in the last t6o decades o. the 20th century and
a*+initio 8B calculations .or chemically interesting molecules are no6 reported on a
regular 3asis7 Concurrently 6ith the rise o. a*+initio 8B calculations a ne6 4id appeared
#?% The Co/alent Chemical Bond
on the 3loc4, density f1nctional theory (<DT+, 6hich ta4es a /ery di..erent approach to
the pro3lem o. calculating the physical properties o. molecules, 3ut appears to hold out
great promise in terms o. 0uality o. results and computational e.Lciency7
The 3i3liography, to 6hich A add some comments here, contains a .e6 leading re.2
erences to this etensi/e and still rapidly ad/ancing Leld o. chemical research7 Le/ine
$
has a long chapter 6hich pro/ides an ecellent introduction to C" methods, 3oth semi+
em%irical and a*+initio, and to <DT7 The 3oo4 3y 9inchli..e
#0
is a compact introduction
to a*+initio C" methods7 T6o /olumes in the 'lse/ier series, -heoretical and Com%1+
tational Chemistry, comprise ad/anced treatments o. modern <DT
##
and 8B
#2
6or4 3y
multiple authors7 Gerratt, a pioneer o. the modern 8B methodology, and some colleagues
ha/e 6ritten a chemistry2orientated re/ie6
#,
o. that theory7
This is also an appropriate place to note an eciting and /ery recent eperimental
ad/ance
#*
3ecause the ne6 techni0ue has pro/ided, .or the Lrst time, an image o. a
molecular or3ital 6hich can 3e directly compared 6ith theoretical results7 Colecular
or3itals are essentially a mathematical construct (Section ?75+, 3ut the .act that so many
eperimental measurements can 3e 0uantitati/ely interpreted 3y C" methods has gi/en us
reason to 3elie/e that they represent much more than that7 ;o6, eperiments using laser
pulses on the .emto2second (#0

#5
s+ time scale ha/e pro/ided an image o. the highest
occupied C" (9"C"+ o. nitrogen (;
2
+ ('
,
in Digure ?7$+ 6hich compares remar4a3ly
6ell, 0uantitati/ely, 6ith a similar image produced 3y an a*+initio C" calculation7 At
should 3e emphasised that the image is o. the C" itsel., not o. the s0uare or electron
density, and 6e see the epected pattern o. phases7 The authors 3elie/e that it 6ill 3e
possi3le to o3tain such images on a time scale 6hich 6ill allo6 us to .ollo6 the change
in electron distri3ution during a chemical reaction I an insight into the /ery essence o.
chemistry7
*1%- 8I85I2RA!HY AN3 6URTHER REA3IN
#7 W7G7 !almer, A 8istory of the Conce%t of Valency to IWXY, Cam3ridge =ni/ersity !ress, #$?57
27 C7A7 :ussell, -he 8istory of Valency, Leicester =ni/ersity !ress, #$-#7
,7 C7A7 Coulson, Valence, 2 nd edn, ".ord =ni/ersity !ress, #$?#7 : CcWeeney, Co1lson6s
Valence, , rd edn, ".ord =ni/ersity !ress, #$-$7
*7 C7S7G7 !hillips and :7J7!7 Williams, :norganic Chemistry, ".ord =ni/ersity !ress, #$?57
57 '7!7 Wigner and D7 SeitK, Solid State Physics, %, $- (#$55+7
?7 J7;7 Currell, S7D7A7 >ettle and J7C7 Tedder, Valence -heory, 2nd edn, Wiley, London, #$-07
-7 J7W7 Linnett, Wave 5echanics and Valency, Cethuen, London, #$?07
%7 J7W7 Linnett, -he Electronic Str1ct1re of 5olec1les, Cethuen, London, #$?*7
$7 A7;7 Le/ine, 31ant1m Chemistry, 5th edn, !rentice29all Anc7, ;e6 Jersey, 20007
#07 A7 9inchli..e, Com%1tational 31ant1m Chemistry, Wiley, Chichester, #$%%7
##7 J7C7 Seminario and !7 !olitKer ('ds+, 5odern Eensity 91nctional -heory, 'lse/ier, Amsterdam,
#$$57
#27 <7L7 Cooper ('d+, Valence /ond -heory, 'lse/ier, Amsterdam, 20027
#,7 J7 Gerratt, <7L7 Cooper and !7B7 >arada4o/, Chem. Soc. Revs., &*, %- (#$$-+7
#*7 J7 Atani, J7 Le/es0ue, <7 Neidler, 97 ;i4ura, 97 !ebpin, J7C7 >ie..er, !7B7 Cor4um and
<7C7
8illeneu/e, Nat1re, ('&, %?- (200*+7
The .ollo6ing three 3oo4s illustrate 6ell the application o. the 0uantum2mechanical theory o.
chemical 3onding to a /ery 6ide range o. real chemical pro3lems, in 6ays 6hich emphasise the
pictorial rather than the mathematical aspects o. the theory7
A / / A
$
2
/
Boes .or Chapter ? #?$
#57 T7A7 Al3right, J7>7 Burdett and C797 Whang3o, 4r*ital :nteractions in Chemistry, Wiley, ;e6
Ror4, #$%57
#?7 ;7W7 Alcoc4, /onding and Str1ct1re Str1ct1ral Princi%les in :norganic and 4rganic Chem+
istry, 'llis 9or6ood Ltd, Chichester, #$$07
#-7 A7 Dleming, 9rontier 4r*itals and 4rganic Chemical Reactions, Wiley, Chichester, #$-?7
82D *1% Normalisation o" t$e Aalen#e ?on/ FV8G an/ mole#;lar or?ital FM2G
waAe ";n#tions "or t$e $0/rogen mole#;le
The 8B 6a/e .unction to 3e normalised is1
= ;Z$
A
!#"$
/
!2" + $
/
!#"$
A
!2"\
A. the 6a/e .unction is normalised then the /alue o. the normalising constant ;
must 3e such that1

2
dv
#
dv
2
= ;
2
Z$
A
!#"$
/
!2" + $
/
!#"$
A
!2"\
2
dv
#
dv
2
= #.0
;
2
{Z$
A
!#"$
/
!2"\
2
+ Z$
/
!#"$
A
!2"\
2
+ 2Z$
A
!#"$
/
!2"\

Z$
/
!#"$
A
!2"\
}
dv
#
dv
2
=
#.0
N
2
$
2
!#" dv
#
$
2
!2" dv
2
+
$
2
!#" dv
#
$
2
!2" dv
2
+
2 $
A
!#"$
/
!#" dv
#
$
/
!2"$
A
!2" dv
2
= #.0
But, 3y deLnition, $
A
and $
/
are normalised #s atomic or3itals o. the hydrogen
atom, i7e71
A
!#" dv
#
= $
2
!#" dv
#
= #.0
There.ore, the Lrst t6o terms o. the epression a3o/e are each e0ual to #70 and
6e ha/e1
;
2
{2 + 2
$
A
!#"$
/
!#" dv
#
$
/
!2"$
A
!2" dv
2
} = #.0
Since all electrons are identical, the t6o integrals in the a3o/e e0uation are e0ual
and they can only ha/e a /alue in the region o. space 6here the atomic 6a/e .unctions,
$
A
and $
/
, 3oth ha/e non2Kero /alues7 A. 6e dra6 3oundary sur.aces .or the t6o A"Gs
separated 3y the 9I9 3ond length (Digure B?7#7#+ then 6e see that this condition is
only .ulLlled 6here the t6o A"s o/erlap7 Dor this reason, integrals o. this 4ind are
called overla% integrals7
The o/erlap integral is usually denoted 3y S1

S = $
A
!#"$
/
!#" dv
#
.
A
.
B
6ig;re 8*1%1% The o/erlap o. t6o #s atomic or3itals
Ta?le 8*1%1% The /alues o. S #s|#s as a .unction o. the or3ital eponent (N+ and
the inter2nuclear distance (:+ in atomic units
: (a
0
+
N 07% #70 #72 #7* #7? #7% 270
07$ 07$2# 07%%2 07%,% 07-$# 07-*2 07?$2 07?*#
#70 07$05 07%5% 07%0- 07-5, 07?$- 07?*# 075%?
#7# 07%%- 07%,, 07--5 07-#* 07?52 075$2 075,,
#72 07%?% 07%0- 07-*2 07?-5 07?0% 075** 07*%,
#7, 07%*% 07-%0 07-0% 07?,? 075?5 07*$% 07*,5
6here the triple integral sign reminds us that this is an integration o/er all three spatial
co2ordinates o. electron #7 Some /alues o. the integral are gi/en in Ta3le B?7#7#7 We
there.ore ha/e1
#
;
2
!2
+
2S
2
"
=
#.0

;
= {
2!#
+
S
2
"
}

2
The C" 6a/e .unction to 3e normalised is1
= ;

{!$
A
+ $
/
"!#"}
A. 6e call the normalisation constant ;

, then .or a normalised C" 6e must ha/e1

2
dv
#
= ;

2
{!$
A
+ $
/
"!#"}
2
dv
#
= #.0

;
2
{
$
2
!#"
+
$
2
!#"
+
2$
A
!#"$
/
!#"
}
dv
# =
#.0
A /
There.ore1
;

2
{2 + 2S} = #.0
#
;

= {
2!#
+
S"
}

2
2
2s 2p
$
2
*

82D *1& !roo" t$at t$e "o;r sp


'
$0?ri/ A2s o" E@;ation F*1%)1'G are normalise/
an/ ort$ogonal
N2RMA5ISATI2N

#
=
#
{$
2s
+ $
2p

+ $
2p
y
+ $
2p
K
}

2
dv
=
#
{
$
2s +
$
2p +
$
2p +
$
2p }
2
dv
#
*
y K
(Dor the sa4e o. simplicity 6e omit the electron in these e0uations7+
When the a3o/e 6a/e .unction is s0uared 6e Lnd terms o. t6o types1
a+ s0uared .unctions such as $
2
and $
2

3+ cross2terms such as $
2s
$
2p

and $
2p

$
2p
y
Since A"s o. the same atom, i7e7 $
2s
$
2p

$
2p
y
and $
2p
K
, are orthogonal and
nor2 malised, the .our s0uared terms each gi/e #70 and the #2 cross2terms each
contri3ute
Kero1
2s
dv = #.0 and $
2s
$
2p

= 0.0
There.ore

2 #
&'<7
#
dv
=
*

*
=
#.0
2RTH22NA5ITY


#

2
dv =
#
{Z$
2s
+ $
2p

+ $
2p
y
+ $
2p
K
\ Z$
2s
$
2p

$
2p
y
+ $
2p
K
\} dv
As 3e.ore, all the cross2terms gi/e Kero7 Dor the .our s0uared terms 6e ha/e1
#

2 2 2 2 #
&'<7
*
{
$
2s

$
2p


$
2p
y
+
$
2p
K
}
dv
=
*
{
#

#

#
+
#
} =
0
82D *1' Slater9T0pe 2r?itals FST2sG
The /ast ma@ority o. the calculations o. molecular 6a/e .unctions, 8B and C",
proceed .rom a 3asis set o. atomic or3itals7 As 6e ha/e seen (Section 57-+, the
radial .unctions o. accurate sel.2consistent2Leld or3itals .or an atom 6ith more than
one electron cannot 3e epressed in analytical .orm and 6ould there.ore 3e totally
impractica3le in general use7 Durthermore, since the electron cloud surrounding each
atom must undergo considera3le changes 6hen 3onds are .ormed, approimate atomic
or3ital .unctions may pro/ide as suita3le a starting point as more accurate ones7 "ne
o. the earliest proposals .or the construction o. suita3le analytical atomic radial .unc2
tions .or calculations on molecules 6as made 3y Slater in #$,0 (J7C7 Slater, Phys.
Rev., '*, 5- (#$,0++ and these .unctions ha/e 3een etensi/ely used, 3oth in their
original .orms and 6ith some modiLcations7 The original .orms ha/e 3een adopted
.or the calculation o. atomic or3ital o/erlap in this chapter7
Slater Lrst made a radical simpliLcation o. the radial .unction 3y proposing a
.unctional .orm 6hich had no nodes as opposed to the n # radial nodes .ound in
the eact 6a/e .unctions (see Chapter 5, Section 27# and Bo 57,+7 9e proposed the
normalised .unctions1

nlm
=

!2O

,n"
2n
+
#

#,2
!2n"U
r
n#
ep!O

r,n" R
lm
!# $"
6here N

is an effective nuclear charge .or a single electron in a central Leld resulting
.rom the nuclear charge and the repulsion o. the remaining electrons in the atom7 The
other sym3ols ha/e the meanings eplained in Chapter 57
Drom an analysis o. atomic spectral data, Slater o3tained a set o. rules .or calcu2
lating the screening, S, o. the electrons 6hich is then su3tracted .rom the true nuclear
charge, N, to gi/e N

(in units o.
+
e+7 S is calculated according to the .ollo6ing
rules1
#7 The electrons are di/ided into groups7 'ach electron in a group has the same
shielding constant 6hich di..ers .rom that o. the electrons in other groups7 The
groups are #sP 2s + 2pP ,s + ,pP ,dP *s + *pP *dP *.P 5s + 5pP etc7
27 The screening constant, S, is then gi/en as a sum o. the indi/idual contri3utions,
s, 6hich are calculated as .ollo6s1
(a+ Dor any electron outside the shell
f
under consideration s
=
0.07
(3+ Dor each other electron in the group considered s = 0.,5, ecept .or the #s
6here s = 0.,07
(c+ A. the group considered is an s + p group then s = 0.%5 .or each electron in
the net inner shell
f
and s = #.00 .or all electrons .urther in7
(d+ A. the group is a d or . group then s = #.00 .or e/ery electron inside it7
The .ollo6ing eamples illustrate the calculation o. N

.or the occupied or3itals
o. the iron atom, (#s+
2
(2s+
2
(2p+
?
(,s+
2
(,p+
?
(,d+
?
(*s+
2
7
Dirst .orm the re0uired electron groups1 Z#s\
2
P Z2s
+
2p\
%
P Z,s
+
,p\
%
P Z,d\
?
P Z*s\
2
7
N

!#s" = 2? !# 0.,0" = 25.-0
N

!2s" = 2? !- 0.,5" !2 0.%5" = 2#.%5 = N

!2p"
N

!,s" = 2? !- 0.,5" !% 0.%5" !2 #.00" = #*.-5 = N

!,p"
f
A shell is the set o. atomic or3itals ha/ing the same principal 0uantum num3er, n7
K
,
N

!,d"
=
2?

!5

0.,5"

!#%

#.00"
=
?.25
N

!*s" = 2? !# 0.,5" !#* 0.%5" !#0 #.00" = ,.-5
Because the .unctions ha/e no radial nodes, ST"s pro/ide a /ery poor description
o. the inner regions o. the atom7 9o6e/er, they are a much 3etter representation o.
the outer atomic regions, and since these are the regions o. most signiLcance .or
chemical 3inding ST"s ha/e 3een 6idely used in theoretical chemistry, though their
use is no6 in decline7 The Slater rules also re0uire that the higher principal 0uantum
num3ers, n, o. *, 5 and ? 3e replaced 3y ,7-
]
, *70 and *72
]
respecti/ely and the
0uality o. the ST"s deteriorates signiLcantly as n rises7 "ne 6ay o. impro/ing on
ST"s is to use a com3ination o. t6o o. them, each 6ith a di..erent /alue o. N

, to
represent one atomic or3ital7 "r3itals o. this type are 4no6n as dou3le2Keta .unctions7
]
The normalisation .actor in the ST" .ormula gi/en a3o/e does not apply .or non2integral /alues o. n7
82D *1( Ele#tron spin #orrelation: An example "ollowing J141 5innett
%
"ur purpose here is to demonstrate in more detail the 6ay in 6hich the !auli principle,
3y allo6ing only 6a/e .unctions 6hich are antisymmetric 6ith respect to electron
echange, eerts an important inOuence upon the energies o. states ha/ing di..erent
multiplicities and also upon the orientation o. electron distri3utions in space7 Suppose
that 6e ha/e an atom 6ith a closed #s electron shell, 6hich 6e ignore, and one
electron in each o. the 2s and 2p
K
or3itals, i7e7 conLguration #s
2
2s
#
2p
#
7 An Section
*7$ it is sho6n that i. the t6o electrons ha/e opposed spins the resulting state is a
singlet state and i. their spins are parallel 6e ha/e a triplet state and that the
spin 6a/e
.unctions o. the states 6ith S
B
=
0 are1
and


spin
!singlet"
=
!#, 2"{L!#"K !2" K!#"L!2"}

spin
!triplet" = !#

2"{L!#"K !2" + K!#"L!2"}.


When the electrons are echanged the sign o. the singlet .unction changes 6hile
that o. the triplet remains the same so that the singlet spin .unction is antisymmetric
6ith respect to electron echange 6hile the triplet is symmetric7 But the !auli prin2
ciple re0uires that the total electronic 6a/e .unction 3e antisymmetric 6ith respect
to electron echange, so to .ulLl that re0uirement the symmetric spin .unction must
3e com3ined 6ith an antisymmetric space .unction, and /ice /ersa7 This is ho6 spin
.unctions determine space .unctions and hence electron repulsion energies and the
su3@ect is eplored in more detail in Section ##757
The appropriate space .unctions are o. /ery similar .orm and 6e choose the sym2
metric .unction .or the singlet and the antisymmetric .unction .or the triplet1


space
!singlet"
=
!#, 2"
{
2s!#"2p
K
!2"
+
2p
K
!#"2s!2"
}
,
,
and

space
!triplet" = !#

2"{2s!#"2p
K
!2" 2%
K
!#"2s!2"}
We must no6 gi/e the indi/idual 2s and 2p
K
.unctions a more speciLc .orm7
The 2s is purely a .unction o. r since it is spherically symmetrical and the 2p
K
is a
.unction o. r multiplied 3y an angular part o. cos # (Appendi 5+7 There.ore, 6e 6rite
2s
=
f
s
!r " and 2p
K
=
f
%
!r "

cos # and assume that the .unctions are normalised7 At
is not necessary to ma4e the .unctions more eact, they already contain the essential
elements as 6e shall see7 Since 6e are concerned 6ith electron repulsion, 6e only
need to study the space .unctions 6hich can no6 3e 6ritten1

and

space
!singlet"
=
!#,

space
!triplet" = !#

2"
{
f
s
!r#"

f
%
!r2"

cos #
2
+
.
%
!r#"

cos #
#

f
s
!r2"
}
2"{f
s
!r#" f
%
!r2" cos #
2
f
%
!r#" cos #
#
.
s
!r2"}
When the t6o electrons are at the same radius, r

say, the epressions a3o/e
3ecome1
and

space
!singlet" = !#,

2"f
s
!r

"

f
%
!r

"
{
cos #
2
+
cos #
#
}


space
!triplet"
=
!#, 2".
s
!r

"

.
p
!r

"
{
cos #
2

cos #
#
}
The electron pro3a3ility is proportional to the s0uare o. the 6a/e .unction 6hich
is at a maimum .or the singlet .unction 6hen #
#
= #
2
= 0 or 6hen #
#
= #
2
= ( 7
Con/ersely, the maimum o. the triplet .unction occurs 6hen #
#
=
0 and #
2
=
(
or /ice /ersa7 Thus, i. the electrons in the 2s and 2p
K
or3itals ha/e a high pro3a3ility
o. 3eing at the same distance .rom the nucleus then, .or the singlet state, the spin
correlation places the electrons on the same side o. the nucleus 6hereas, .or the triplet
state, the most li4ely position .or the electrons is on opposite sides o. the nucleus7 The
hydrogen atom radial electron density .unctions illustrated in Digure 57, sho6 a /ery
mar4ed o/erlap o. the 2s and 2p .unctions so that 6e may epect spin correlation
to play an important role in the determination o. molecular geometry7 Durthermore,
it is clear that the interelectronic repulsion o. the electrons is lo6er in the triplet
state than in the singlet7 This illustrates the underlying reason .or 9undGs rule and
in/ites us to en0uire .urther into the theoretical .oundations o. the 8S'!: method
(Section ?7#-7#+7
An Section ##75 6e sho6 that the electron2repulsion energy o. the singlet and triplet
states deLned a3o/e are gi/en 3y1
E
triplet
= Q
2s2p
@
2s2p
and E
singlet
= Q
2s2p
+ @
2s2p
6here Q
2s2p
= 2s!#"2p!2"|#,r
#2
|2s!#"2p!2"
and @
2s2p
= 2s!#"2p!2"|#,r
#2
|2p!#"2s!2" .
The electron repulsion Q
2s2p
is called the Coulom3ic repulsion and represents the
classical repulsion o. t6o electrons, one in the 2s or3ital and the other in the 2p7
The repulsion @
2s2p
is called the echange repulsion and ma4es a contri3ution to
the interelectronic repulsion 6hich has no classical counterpart7 Though @
2s2p
itsel.
is a positi/e 0uantity, the .act that it appears 6ith a negati/e sign in the epression
.or E
triplet
should alert us to its non2classical nature7 At represents the repulsion o.
the t6o electrons in the o/erlap regions, i7e7 electron density 2s(#+2p(#+ repelling
density 2s(2+2p(2+7 Such a term can only arise in 0uantum mechanics 6here electron
pro3a3ility is gi/en 3y the s71are o. a .unction, not 3y the .unction itsel.7 The presence
o. such a term in the epression .or repulsion energy immediately con.ronts us 6ith
a /ery .undamental 0uestion7 Are 6e @ustiLed in tal4ing a3out electron2pair repulsion
in molecules in purely classical termsJ
Calculations 3y J7 Lennard2Jones and J7A7 !ople
2
thro6 some light upon that
0uestion7 They used Slater2type or3itals (Bo ?7,+ to calculate the /alues o. Q
2s2p
and @
2s2p
, in atomic units, .or the 3eryllium atom and .ound the /alues sho6n in
Ta3le B?7*7#7 N

is the e..ecti/e nuclear charge7
The data in the Lrst ro6 o. the ta3le sho6 that the non2classical term is a3out
22 Y o. the classical term 6hich pro/ides some @ustiLcation .or our neglect o. it 6hen
6e apply the 8S'!: theory7 The /alues in the second ro6 are also rele/ant to this
discussion, 3ut they Lrst re0uire .urther eplanation7 Drom the 2s and 2p or3itals 6e
can .orm normalised hy3rid or3itals (called e71ivalent or3itals 3y Lennard2Jones and
!ople+ o. the .orms1

h
+
=
!#, 2"{2s + 2p
K
} h

= !#,

2"
{
2s

2p
K
}
and i. 6e calculate Q and @ 6ith these hy3rids 6e o3tain the results in the second
ro6 o. the ta3le7 We Lrst note that the total electron repulsion energy, Q @ , is
constant, independent o. the change to hy3rid or3itals, 6hich is 0uite generally true
as Lennard2Jones and !ople
2
pro/e7 The .ormulation o. the electron distri3ution in
terms o. hy3rids reduces the non2classical term .rom 22 Y to 27* Y o. the classical7
Clearly, in this case, a classical /ie6 o. electron repulsion is more @ustiLed 6hen
hy3rids rather than the 2s and 2p or3itals themsel/es are used7 The same is true in
other situations, e7g7 .our sp
,
hy3rids as opposed to a 2s and three 2p or3itals, though
the di..erence is less mar4ed7 The reason .or the decrease in the magnitude o. @
6hen hy3rid or3itals are used is the reduction o. the o/erlap electron densities due
to the localised and directional character o. the hy3rids7 At is .ortunate, there.ore,
that the localised groups o. 3onding or lone2pair electrons 6hich 6e en/isage 6hen
6e apply the 8S'!: method are @ust those electron distri3utions in space 6hich 6e
also associate 6ith hy3rid or3itals7 Though it is not essential to in/o4e hy3ridisation
6hen applying the 8S'!: theory, it does appear that hy3rid or3itals ma4e a classical
approach to electron repulsion more accepta3le .rom a strictly 0uantum2mechanical
point o. /ie67
Ta?le 8*1(1% 'lectron repulsion integrals .or Be1 #s
2
2s
#
2p
#
Q
a3
,E
9
@
a3
,E
9
!Q
a3
@
a3
",E
9
a = 2s, 3 = 2p 07#%#? N

070*0# N

07#*#5 N

a
=
h+ 3
=
h 07#*50 N

0700,5 N

07#*#5 N

2
#
RE6ERENCES
#7 J7W7 Linnett, Wave 5echanics and Valency, Cethuen, London, #$?07
27 J7 Lennard2Jones and J7A7 !ople, Proc. Roy. Soc., A&.&, #?? (#$50+7
!R285EMS 62R CHA!TER *
#7 =se the .ollo6ing data to dra6 an energy2le/el diagram, similar to Digure ?7#, .or the
-
Li
2
molecule7 Calculate E
e
7
Li Li
+
+ e A' = 5.,$ e8 *,*-, cm

#
Li
2
Li + Li E
0
= #.0, e8 %,0- cm

#
Nero2point energy =
#
h> = 0.022 e8 #-5.- cm

#
27 !7 Corse proposed that, .or a diatomic molecule, the /ariation o. the energy (E+ 6ith
internuclear distance (r + could 3e 6ritten1
E = E
e
Z# ep{K!R
e
r"}\
2
Dor Li
2
R
e
, the e0uili3rium internuclear distance = 2?-., pm and K is a constant related
to the /i3rational .re0uency (>+ o. the molecule and the reduced mass (T+1
m
#
m
2
,.50$ a7m7u7 K
=
*.0?#-

#0

*

>

#
T

2
T
=
!m + m
2
"
=
E
e
(The last epression gi/es K in cm

#
6hen T is entered in a7m7u7, > in s

#
and E
e
in cm

#
7+
!lot the Corse cur/e .or Li
2
.or r
=
5 I #?0 nm using the data a3o/e7 (This is
a pro3lem 6here a spread sheet 6ith a graph2plotting .acility, e7g7 'FC'L, is /ery
use.ul7+
,7 The .unction $ is a normalised #s atomic or3ital7
#
$
=
(

O

,,2
a
0
ep!Nr,a
0
" a
0
= Bohr radius = 52.$2 pm
Allustrate the etension o. the or3ital into the space surrounding the atom 3y plotting
the .unction $ /ersus r .or N = 0.5, #70, #757 (9ere, again, a spread sheet can 3e /ery
use.ul7+
*7 Sho6 that the sp
2
hy3rid or3itals ('0uation (?7#57*++ are normalised, orthogonal and
orientated at #20

to each other7 (8ector alge3ra, regarding a normalised p2or3ital as a
unit /ector along the appropriate ais, or trigonometry can 3e used .or the orientation
pro3lem7+
57 This pro3lem is essentially a repeat o. 9eitler and LondonGs Lrst 8B calculation o. the
3inding energy o. the hydrogen molecule7 We 6or4 in atomic units 6hich are much
easier to use in calculations7 The energies 6hich 6e determine can 3e easily con/erted
to SA energy units, i. that is re0uired7
!ro3lems .or Chapter ? #--
9

An a7u7 the 9amiltonian (9



+ o. '0uation (?7,7#+ 3ecomes1
# 2 # 2
# # # # # # =
2

#

2

2

r A#

r
B#

r
A2

r
B2
+
r
#2
+
R
AB
#
Rou 6ill Lnd it use.ul to note that a pair o. terms such as

#

or

#

2
2 #
r A#
2 #
#
r B#
constitute the 9amiltonian operator .or a hydrogen atom7 There.ore, i. 6e denote
such a pair 3y 9

#s
and a hydrogen #s or3ital 3y $
A
then1
9

#s
$
A
!#" = E
#s
$
A
!#"
The 8B 6a/e .unction ('0uation (?7*7,++ is1
= ;{$
A
!#" $
B
!2" + $
B
!#" $
A
!2"}
6here the normalising constant (;+ is determined in Bo ?7#7
Sho6 that the epectation /alue o. the energy (E+ is gi/en 3y1
E
=
G |9

|G Q + @
Where1
G |G
=
# + S
2
Q

= 2E
#s
+ 23 + Q + #,R
AB
@

= 2S
2
E
#s
+ 2S3

+ @ + S
2
,R
AB
3 = $
A
!#"| #,r
B#
|$
A
!#" 3

= $
A
!#"| #,r
B#
|$
B
!#" S = $
A
!#"|$
B
!#"
Q = $
A
!#" $
B
!2"|#,r
#2
|$
A
!#" $
B
!2" and
@ = $
A
!#" $
B
!2"|#,r
#2
|$
B
!#" $
A
!2"
Sho6 that i. 6e set 2E
#s
= 0.0 then the di..erence in energy ( E+ 3et6een the
molecule and t6o hydrogen atoms is1
23
+
2S3

+
Q
+
@ #
E =
# + S
2
+
R
AB
Sho6 that the trial 6a/e .unction, G

= $
A
!#" $
B
!2", is normalised and gi/es an
epectation /alue .or the energy o.1
E

=

G
|
9
|
G

G

|G


=
Q
=sing the data in the .ollo6ing ta3le, plot graphs o. E and E

against internuclear
distance, R
AB
7 The result sho6s that the 3inding energy o3tained 6ithout allo6ing .or
electron QechangeG is a3out one2sith o. that o3tained 6ith the .ull 6a/e .unction7 But
the 6a/e .unction G

is 0uite unaccepta3le since it contradicts the .undamental theo2
retical re0uirement that 3oth terms, $
A
!#"

$
B
!2" and $
A
!2"

$
B
!#", must 3e included
3ecause electrons are indistinguisha3le7
R
AB
,a
0
0.25
S
0.$%$-,
3,E
9
0.$?-,5
3

,E
9
0.$-,50
Q ,E
9
0.?#$%?
@,E
9
0.?0$-*
0.-5 0.$#52#
0.%#2-0 0.%2??*
0.5%25$ 0.50?%*
#.25 0.-$,%?
0.?5225 0.?**?*
0.52,#, 0.,?*-$
#.50 0.-25#-
0.5%,?$ 0.55-%,
0.*$0,* 0.2$?%*
#.?5 0.?%,22
0.5*?%2 0.50%$,
0.*-0?# 0.25$*0
#.-5 0.?552-
0.52,$% 0.*--%%
0.*5-?0 0.2,?#2
2.00 0.5%?*5
0.*-25, 0.*0?0#
0.*25$- 0.#%*#?
2.50 0.*5%,#
0.,$05- 0.2%-,0
0.,?%,$ 0.#0??2
,.00 0.,*%5#
0.,,00, 0.#$$#5
0.,#$%0 0.05%5#
,.50 0.25$#$
0.2%*5* 0.#,5%$
0.2-$$* 0.0,0-?
*.00 0.#%$2?
0.2*$5% 0.0$#5%
0.2*-55 0.0#5?0
*.50 0.#,?0$
0.2220- 0.0?##0
0.22##$ 0.00-?0
5.00 0.0$?5%
0.#$$$5 0.0*0*,
0.#$$5- 0.00,#%
Dind the epectation energy, E

, .or the 6a/e .unction G

, 6hich represents an
unsta3le state o. 9
2
1
G

= ;

{$
A
!#" $
B
!2" $
A
!2" $
B
!#"}
!lot E

against R and compare the cur/e 6ith your results .or G and G

7
?7 Consider the molecule sho6n in the Lgure1
#
3
9
3
2 9
g
9
,
9ydrogen atoms 2 and , o. the 9
,
molecule are e0ually 3onded to atom # 3ut the
3ond 3et6een 9# and 92 is not necessarily o. the same strength and this is reOected
in the /alues o. the interaction elements o. the energy (9amiltonian+ matri1
$
#
|9

|$
2
= $
#
|9

|$
,
= K 3ut $
2
|9

|$
,
= N
6here $
n
is a hydrogen #s A" on atom n7 ;ote that K and N are negati/e 0uantities
3ecause they represent 3onding interactions 6hich reduce the energy o. the molecule
vis+aZ +vis the isolated atoms7 A. 6e ar3itrarily L the Kero o. the energy scale 3y
setting the on2diagonal elements o. the matri to L 6e ha/e1
9

$
#
$
2
$
,
$
#
L K K
$
2
K L N
$
,
K N L
Dind the eigen/alues o. this matri (Appendi ,+7 (A. you .orm ro6s and columns
o. $
#
!$
2
+ $
,
",

2 and !$
2
$
,
",

2 you 6ill Lnd that the matri 3loc4s out into a


# # and a 2 2 matri7+
T6o etreme .orms o. the molecule may 3e en/isagedP one (the linear molecule+
in 6hich N 0 and the other in 6hich N = K (the e0uilateral triangle+7 <etermine the
eigen/alues .or these t6o species7
=se a spread sheet to plot a correlation diagram relating the molecular or3ital
energies o/er the 6hole range o. relati/e /alues o. K and N 7 (At is con/enient to set
L = 0.0 K = #0.0 and N = 0.0 to #070 in steps o. #707+
A. the energies o. the molecular or3itals o. an 9
,
species 6ere measured and .ound
to 3e *72 e8, +07% e8 and +,7* e81
(a+ Where on the correlation diagram should the molecule 3e placedJ
(3+ What 6ould the relati/e /alues o. K and N 3eJ
(c+ What 6ould the a3solute /alues o. K and N 3eJ
ZAns6ers1 (a+ N = ,P (3+ N ,K = 0.,P (c+ K = 2.?-, N = 0.%\
Chapter -
8on/ing< Spe#tros#op0 an/
Magnetism in Transition9Metal
Complexes
-70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%#
-7# 9istorical de/elopment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%2
-72 The crystal Leld theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%2
-7, The electronic energy le/els o. transition2metal complees . . . . . . . . . . . . #%-
-7,7# The 6ea42Leld scheme .or d
2
(eample o.
,
D in an octahedral Leld+ . #%$
-7,72 The 6ea42Leld scheme .or d
2
(inclusion o.
,
!+ . . . . . . . . . . . . . . .
-7,7, The d
2
energy le/els .or 6ea4, strong and intermediate
#$0
octahedral Lelds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #$#
-7,7* The strong2Leld scheme .or d
2
in an octahedral Leld . . . . . . . . . . . #$,
-7,75 Spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #$5
-7* The electronic spectroscopy o. transition2metal complees . . . . . . . . . . . . #$?
-75 !airing energiesP lo62spin and high2spin complees . . . . . . . . . . . . . . . . . #$-
-7? The magnetism o. transition2metal complees . . . . . . . . . . . . . . . . . . . . . #$-
-7- Co/alency and the ligand Leld theory . . . . . . . . . . . . . . . . . . . . . . . . . . #$$
-7% Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20,
!ro3lems .or Chapter - . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#2
+1. INTR23UCTI2N
The colours and magnetic properties o. the comple compounds o. the transition2metal
ions presented a great challenge to the theory o. the chemical 3ond and, although the
pro3lem is no6 6ell understood in principle, 0uantitati/e interpretation o. the many su3tle
e..ects continues to engage the theoretician, not least on account o. their signiLcance
in 3iology and technological applications7 "ne thin4s, .or eample, o. transition2metal
catalysts, the 3iological .unctions o. metallo2proteins, magnetic storage de/ices and up2
con/erters7 9istorically, the interpretation o. these phenomena has 3een 3y means o. ligand
Leld (LD+ theory, 3ut density .unctional theory and UL scattered26a/e methods are no6
seeing increasing application7 The 6ords Qligand Leld theoryG con/ey to the practitioners
a range o. methods, /arying 6idely in their sophistication, o. applying e..ecti/ely the
same theory7 The essentials o. the theory are its origins in crystal Leld (CD+ theory,
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
#%2 Transition2Cetal Complees
etensi/e and sometimes ad/anced use o. group theory and the treatment o. the interaction
3et6een metal ion and ligand as co/alent as 6ell as electrostatic7 A 3rie. outline o. the
de/elopments 6hich ha/e led to the present state o. the art 6ill ma4e these points clearerP
3ut Lrst a comment on the use o. group theory and matri diagonalisation7
The theory o. the transition2metal ions relies hea/ily upon group theory and many
ecellent descriptions o. the su3@ect 6hich incorporate the re0uired group theory are
a/aila3le7
#
At there.ore appears superOuous to include group theory here and little or no
appeal to it 6ill 3e made in the .ollo6ing chapter7 The use o. group2theoretical sym3ols
to identi.y electronic states should present no pro3lemsP the reader 6ho has no 4no6ledge
o. the su3@ect may regard these sym3ols simply as la3els7
An 6hat .ollo6s 6e shall also ma4e .re0uent appeal to the concept o. determining
energies 3y setting up and diagonalising the 9amiltonian matri .or a pro3lem7 :eaders
un.amiliar 6ith this idea should read Appendi , 3e.ore going 3eyond Section -7#7
+1% HIST2RICA5 3EVE52!MENT
An #$2$, J7 Bec0uerel proposed that the central metal ion in a transition2metal comple
6as su3@ect to an electrostatic Leld originating .rom the surrounding ligands7 An the same
year, 9ans Al3recht Bethe (#$0? I + used symmetry and group theory to place
Bec0uerelGs idea on the Lrm theoretical .oundation 6e no6 call CD theory7 Just three
years later, in
#$,2, John 9as3rouc4 8an 8lec4 (#%$$ I #$%0+ demonstrated the po6er o. the ne6
theory 6hen he interpreted the paramagnetism o. the Lrst2ro6 transition2metal
complees and the rare earths 6ith good 0uantitati/e accuracy7 8an 8lec4 and his co2
6or4ers made many other seminal contri3utions to the de/elopment o. the theory and its
applications o/er the .ollo6ing decade7
A /alence 3ond approach to the pro3lem 6as introduced in the #$*0s 3y Linus !auling,
3ut it pro/ed less success.ul than the CD theory in the interpretation o. electronic spectra
and 6e shall not pursue it .urther here7 At is descri3ed in detail in !aulingGs masterpiece,
-he Nat1re of the Chemical /ond7
2
With the gro6th o. the molecular or3ital (C"+ theory in the second hal. o. the 20th
century, the time appeared ripe to tac4le the most o3/ious shortcoming o. the CD theory7
The interaction 3et6een ligand and central metal ion is clearly more than a purely elec2
trostatic oneP there is also a signiLcant element o. co/alency 6hich should 3e amena3le
to a C" treatment7 The range o. theories 6hich gre6 .rom this seed carry the collecti/e
name o. ligand Leld theory7
+1& THE CRYSTA5 6IE53 THE2RY
Cany o. the complees o. the transition metal ions are /ery symmetrical7 Bethe sho6ed
ho6 the symmetry could 3e elegantly eploited 3y means o. group theory to determine the
6ay in 6hich a purely electrostatic Leld .rom the surrounding ligands could remo/e the
L/e2.old degeneracy o. the partially occupied metal d or3itals7 As noted a3o/e, there are
many ecellent accounts o. this su3@ect7
#
As an illustration o. the 0uantitati/e e..ect o. a
crystal Leld on L/e d or3itals 6e shall calculate the matri elements o. an octahedral Leld7
An electron 6ith charge e and polar coordinates r, # and $ and a point charge 0
at r
0
, #
0
and $
0
is sho6n in Digure -7#7 The atomic nucleus is at 0,0,0 and the distance
0
0
0

The Crystal Dield Theory #%,


0
r
0
0
0
.
0
d
;ucleus
e
r 0 .
6ig;re +1% An electron in the Leld o. a negati/e electrostatic charge
3et6een the point charge and the electron is d7 We 6ish to calculate the energy o. each o.
the L/e d2electron distri3utions in the electrostatic Leld o. an array o. si such charges,
0, located at the /ertices o. a regular octahedron7 We shall arrange our results in the .orm
o. a matri, i7e7 6e shall calculate the matri elements o. the crystal2Leld 9amiltonian,
9

c.
7 Dor the single charge in Digure -7# 6e re0uire1
G
n

l

m

|0e,d |G
nlm
= 0e G
n

l

m

|#,d |G
nlm

.or all possi3le com3inations o. t6o d2or3itals7 The 3rac4ets, | and | , imply integra2
tion o/er the electronic coordinates r, # and $7 We use m rather than m
l
to reduce the
compleity o. the notation 6here there is no possi3ility o. con.usion7
"ur Lrst step is to epress the in/erse distance (#,d + in terms o. the spherical harmonics
(Appendi 5+7 R
4L
!# $" descri3es the position o. the electron, .or 6hich the co2ordinates
# and $ can /ary o/er their 6hole ranges, and R
4L

!#
0
$
0
" that o. the charge 6hich is
stationary at the point r
0
#
0
$
0
7 The result is1
,
#

*( r
4
L
=+
4

R
4L
R

(-727#+
d
=
4=0
24 + #

r
4
+
#

L=4
!# $"

4L
!#
0
$
0
"
6here 6e ha/e assumed that the charge is .urther .rom the nucleus than the electron at all
points o. the latterGs distri3ution, i7e7 r
0
is al6ays greater than r7 This is not essential 3ut
it simpliLes the present pro3lem 6hile retaining the essentials o. the method7 Anserting
the epression .or #,d , our matri element 3ecomes1

0e


*( #
L=+4
G
n

l

m



G
nlm
4
n

l

m

4L
0 0
nlm


d

= 0e
4=0
24 + #

r
4
+
#

G
L=4
|r R
!# $"

R
4L
!# $ "
|
G
(-727,+
Because the 3rac4ets, | and | , imply integration o/er the electronic coordinates r, #
and $, 6e can ta4e R
4L

!#
0
$
0
" outside the integration and 6rite1

0e


*( #
L=+4
G
n

l

m



G
nlm 7 7

4
n

l

m

4L
nlm


d

= 0e
4=0
24 + #

r
4
+
#

L=4
R
4L
!# $ " G
|r R
!# $"|G
L=+4
= 0e



A
4L

G
n

l

m

|r
4
R
4L
!# $"|G
nlm

(-727*+
4=0 L=4
+
0
4L
6here
*(
A
4L

24 #
#
r
4+# R

!#
7
$
7
" !-.2.5"
But each 6a/e .unction, G
nlm
, can 3e 6ritten (Section 57*+ as a product o. a spherical
harmonic !R
lm
!# $"" and a radial part (:
nl
(r++ and 6e can separate the radial and
angular integrations7 We then ha/e, simpli.ying the notation 3y dropping the (# , $+ .rom
R
lm
!# $"1

G
n

l

m

|r
4
R
4L
|G
nlm

=

:
n

l

|r
4
|:
nl

R
l

m

|R
4L
|R
lm

r
4

4L
(-727?+
6here r
4
is the epectation /alue o. the 4th po6er o. the distance o. the electron .rom
the nucleus and
4L
stands .or the angular integral7 We no6 eamine the angular integral
in detail in order to ma4e use o. symmetry and the properties o. the spherical harmonics
to reduce the sums o/er L and 47
Dor d or3itals l

=
l
=
2 and, as 6e 4no6 .rom Chapter , ('0uation (,7?7#++, the com2
3ination (coupling+ o. R
2m
!# $" 6ith R
2m

!# $" gi/es the .unctions R
l

m

!# $",
6here !2 2" l

!2 + 2", i7e7 l

can only ta4e the integer /alues 0 to *7 The angular
integral then reduces to a sum o. terms o. the .orm R
l

m

|S
4L
and since the spherical
harmonics
are a set o. orthogonal .unctions, it 6ill 3e non2Kero only .or /alues o. 4 o. 0, #, 2, ,
and *7
A .urther property, the parity, o. the integral

R
2m

|
R
4L
|
R
2m

can no6 3e used to
limit the possi3le /alues o. 4 e/en .urther7 Dor an integral to 3e non2Kero the integrand,
S
2m


R
4L

R
2m
in our case, must 3e e/en7 The parity o. a spherical harmonic R
lm
is
odd
or e/en depending on 6hether its lo3es change sign or retain their sign on in/ersion in
the origin o. coordinates so that the .unction is odd 6hen l is odd and e/en 6hen l is
e/en or Kero7 The d or3itals (l = 2+ are e/en (see Digure 57?+7 At .ollo6s there.ore, since
odd odd = e/en e/en = e/en 6hile odd e/en = odd, that 6hen 4 is odd,
4L
is
Kero and /alues o. 4 = # or , result in an integral o. Kero7 These /alues o. 4 can there.ore
3e neglected7
Thus our d2electron matri element can 3e epressed as a sum o. L.teen terms1

0e

L=+2 L=+*
G
n

2m


n2m
00
0
00 2L
2
2L *L
*
*L
d
G
= 0e
A r
+ A r
L=2
+ A r
L=* (-727-+
This epression can 3e used to calculate the d2electron matri elements .or any arrange2
ment o. charges surrounding a metal ion7 'ach o. the surrounding charges 6ill gi/e a
contri3ution o. the a3o/e .orm to each matri element7 The contri3ution .rom each charge
6ill 3e characterised 3y the di..erent /alues o. the A
4L
corresponding to the particular
/alues o. r
0
, #
0
and $
0
.or that charge7 The /alues o. the
4L
6ill 3e unchanged7
But 6here the disposition o. the surrounding charges is highly symmetrical the num3er
o. terms in the summation can 3e reduced .urther 3y placing restrictions on the possi3le
/alues o. L, as 6ill no6 3e demonstrated .or the case o. an octahedral Leld7 An octahedral
comple 6ith identical charges o. 0 at the ends o. the three Cartesian aes is sho6n in
Digure -727 The relationship 3et6een the polar and Cartesian coordinate systems is sho6n
in Appendi -7
Since the si charges are identical and the electron density o. a d2electron 6a/e .unction
(in its comple .orm+ is cylindrically symmetrical 6ith respect to rotation a3out the N
ais, the contri3ution to a matri element o. the charge at
+
F (polar coordinates r
0
, (,2,
0+ 6ill 3e e0ual to that o. the charge at
+
R !r
0
(,2 (,2"7 Thus, the /alues o. the A
4L


+N
R
F
+F
+R
N
6ig;re +1& An atom surrounded 3y an octahedral array o. negati/e electrostatic charges
at these t6o positions must 3e e0ual7 Since the only di..erence 3et6een the t6o positions
is in the /alue o. $
0
, 6e need eamine only that part o. the epression .or A
4L
6hich is
!$
0
"
=
ep!

iL$
0
"
=
cos L$
0
+
i sin L$
0
7 We ha/e1
at + F A
4L
!0" = cos 0 + i sin 0
and at + R A
4L
!L(,2" = cos L(,2 + i sin L(,2
The t6o /alues o. A
4L
can only 3e e0ual 6hen L( H2 is e0ual to Kero or an integer
multiple o. 2( 7 There.ore, L = 0 * % . . . , and since the upper limit o. |L| is * 6e
ha/e no6 restricted the possi3le /alues o. L to @ust three, 0 and *, gi/ing1

0e
G
n

2m

n2m
00
0
00 20
2
20 *0
*
*0
*
**
** **
*
**

d

G
= 0e A r + A r + A r + A r + A r
Durthermore, simple e/aluation sho6s that A
**
= A
*

*
.or each o. the .our possi3le
/alues o. $
0
!0 (,2 ( " so that1

0e
G
n

2m
n2m
00
0
00 20
2
20 *0
*
*0 **
*
** **
d

G
= 0e A r + A r + A r + A r ! + "
We are no6 in a position to calculate and ta3ulate (Ta3le -7#+ the /alues o. A
4L
and

4L
, 6hich 6e need to e/aluate the re0uired matri elements7 The /alues o. A
4L
can 3e
readily o3tained 3y su3stituting appropriate /alues o. #
0
and $
0
into '0uation (-7275+7 At
is con/enient to sum the columns o. A
4L
/alues in the ta3le 3ecause, .or any particular
matri element, the angular integral,
4L
, is independent o. the position o. the charge7
An e/aluating and ta3ulating the angular integrals,

R
2m

|
R
4L
|
R
2m

, it is use.ul to recall
that the integration o/er $ is Kero unless m
+
L

m

=
0 (see Bo -7#+ and, there.ore,
that 6e ha/e only diagonal matri elements, ecept 6here L = *7 By 6riting out the
spherical harmonics in their .ull alge3raic .orms (Appendi 5+ and a rather tedious, 3ut
straight2.or6ard, integration (Bo -7#+ 6e o3tain Ta3le -727
At no6 remains to com3ine the results o. Ta3les -7# and -72 to o3tain the re0uired
matri elements7 We Lnd the .ollo6ing, 6here

?0er
#
and

0er
*
r
5
7
0 0
4 = 0 4 = 2 4 = *
R
20
|R
40
|R
20
#,2

(

!5,( ",- ,,-

(
R
2#
|R
40
|R
2#

#,2

(

!5,( ",#*
2,-

R
22
|R
40
|R
22

#,2

!5,( ",- #,#*

(

R
22
|
R
4*
|
R
22

0 0

!5,#*(




Ta?le +1% 8alues o. A
4L
.or an octahedral comple
#
0
$
0
A
00
A
20
A
*0
A
**
+F (,2 0 2

( r
0

#
+R (,2 (,2 2

( r
0

#
+N 0 0 2

( r
0

#
F (,2 0 2

( r
0

#
R (,2 (,2 2

( r
0

#
N ( 0 2

( r
0

#
!(,5" r
0

,
! (,*" r
0

5
!,5(,2%%" r
0

5
!(,5" r
0

,
! (,*" r
0

5
!,5(,2%%" r
0

5
2

!(,5" r
0

,
2

!(,," r
0

5
0

!(,5"

r
0

,
! (,*"

r
0

5
!,5(,2%%"

r
0

5
!(,5" r
0

,
! (,*" r
0

5
!,5(,2%%" r
0

5
2

!(,5" r
0

,
2!

(,," r
0

5
0
Sum #2

( r
0

#
0 -!

(,," r
0

!,5(,#%" r
0

5
Ta?le +1& 8alues o. the non2Kero angular integrals .or an octahe2
dral comple
(
"
The 9amiltonian matri .or the L/e d or3itals in an octahedral crystal Leld7
9

c.
G
20
|
|G
20

+
|G
2#

0
|G
2+#

0
|G
22

0
|G
2+2

0

G
2#
|
0 2 ,, 0 0 0

G
2+#
|
0 0 2 ,, 0 0

G
22
|
0 0 0 + ,? 5 ,?

G
2+2
|
0 0 0 5 ,? + ,?
"n eamining the a3o/e matri 6e see that the term occurs in e/ery diagonal
element7 At represents a uni.orm increase in energy 6hich all L/e d or3itals eperience as
a result o. the surrounding si negati/e charges7 A. 6e set this common term aside .or a
moment, 6e Lnd that the diagonal elements ha/e the /alues !G
20
"

2 H, (G
2#
+ and
H? (G
22
+7 The o..2diagonal matri element 6hich connects the or3itals 6ith m
=
2
is 5 H? and 6hen 6e diagonalise the 2 2 matri 6e Lnd eigen/alues o. and 2 H,7
The .ollo6ing signiLcant results o. the .oregoing calculation may no6 3e noted1
The e..ect o. the octahedral Leld is to raise the energy o. all the d or3itals to a ne6
centre o. energetic gra/ity at 7
Core importantly, it splits the or3ital energies into t6o groups, one t6o.old degenerate
and one three.old7 Dor the dou3ly degenerate (group theoretical sym3olP e
g
+, E =

+
and .or the triply degenerate (group theoretical sym3olP t
2g
+ E
=


2 H,7
The energy2le/el splitting o. 5 H, is usually gi/en the sym3ol and, since it is such
common practice, 6e shall epress energies in terms o. rather than here7 The ne6,
raised centre o. gra/ity is not changed 3y the splitting7
The 'lectronic 'nergy Le/els o. Transition2Cetal Complees #%-
y
Since there is an o..2diagonal matri element 3et6een G
22
and G
2+2
these t6o .unc2
tions are mied in e0ual proportions 3y the crystal Leld to gi/e the or3itals 6hich
6e call G
y
and G

y
2 7 These are the one2electron eigen.unctions o. the 9amiltonian
operator 6hen it includes the octahedral crystal Leld7
There is no o..2diagonal matri element connecting the t6o .unctions G
2

#
and G
2
+
#
so these .unctions are not mied 3y an octahedral Leld7 9o6e/er, 6e generally Lnd
it con/enient to thin4 o. them in terms o. the t6o mied eigen.unctions G
K
and G
yK
6hich ha/e the same energy as G
2

#
and G
2
+
#
7
The e
g
or3ital set 6ith energy + , H5 is1
G
K
2 = G
20
and G

2 2 = !#,

The t
2g
or3ital set 6ith energy 2 H5 is1
2" !G
22
+ G
2+2
"
G
y
= !i,

2" !G
2
G
yK
= !i,

2" !G
2
2
G
#
+ G
2+2
2+#
" G
K
"
= !#,

2" !G
2#
G
2+#
" and
A. 6e imagine the d or3itals in their real .orm (Digure 57?+ then it is easy to see,
0ualitati/ely, 6hy those .or 6hich the lo3es point directly to6ards the point charges,
G
K
2 and G

y
2 , are raised more in energy that those 6here the lo3es point 3et6een
the charges, G
y
G
K
and G
yK
7 At is .ar .rom o3/ious 6hy the energies o. the G
K
2 and
G

y
2 , are raised e0ually, 3ut our 0uantitati/e calculation sho6s that this is indeed
the case7
An principle, an attempt might 3e made to e/aluate the matri elements eactly7 But this
is /ery di.Lcult on account o. our poor 4no6ledge o. the electron distri3ution 6hich
is re0uired to e/aluate the terms in r
*
7 Durthermore, the point charge model is a
/ery
approimate one and it is unli4ely that the 0uantitati/e results o3tained 6ould @usti.y
the e..ort o. calculating them7 The CD model is there.ore used in a 0ualitati/e manner
as eamples o. its applications 3elo6 6ill sho67
Similar calculations can 3e carried out .or any num3er and disposition o. charges
around a central metal ion7 The results o. such calculations .or e0ual charges placed at
the /ertices o. a cu3e, an octahedron and a tetrahedron are illustrated in Digure -7,7 ;ote
that the increase in the centre o. gra/ity is directly proportional to the num3er o. charges
so that cu3e 1 octahedron 1 tetrahedron = * 1 , 1 27 The splittings o. the le/els are
not simply related to the num3er o. chargesP cu3e 1 octahedron 1 tetrahedron, are
in the ratio % 1 $ 1 *7 The displacement o. the triply degenerate le/els (t+ .rom the
centre o. gra/ity is al6ays 2 H5 and that o. the dou3ly degenerate le/els (e+ is al6ays ,
H5, so the centre o. gra/ity is maintained7 ;ote ho6e/er, that in the cu3e and the
tetrahedron E!t" R E(e+ 6hereas in the octahedron E!t" P E(e+7
+1' THE E5ECTR2NIC ENERY 5EVE5S
26 TRANSITI2N9META5 C2M!5EDES
The CD theory, as 6e ha/e descri3ed it a3o/e, is a one2electron theory 6hich immediately
pro/ides a 0ualitati/e interpretation o. the .act that most transition2metal complees are
Cu3e
"ctahedron Tetrahedron
'nergetic c o. g
t
Cu3e
e
'nergetic c o. g
e
"ctahedron
t
'nergetic c o. g
t
Cu3e "ctahedron Tetrahedron
Tetrahedron
e
6ig;re +1' d2'lectron energy le/els Lelds in cu3ic, octahedral and tetrahedral symmetry
coloured, i7e7 they a3sor3 radiation in the /isi3le region 6hich lies at the lo62energy
end o. the electronic spectral range7 Dor eample, an a0ueous solution o. the Ti
,
+
ion
(conLguration1 Ar ,d
#
+ is red and 6e ascri3e the colour to the a3sorption o. green light 3y
a transition o. the single d2electron .rom the t
2g
le/els to the e
g
in the octahedral comple
ZTi(9
2
"+
?
\
,
+
7 This idea can 3e etended to ions 6ith more electrons 3ut, as 6e ha/e seen
in Chapter 5, 6e cannot descri3e the electronic spectra o. atoms 6ithout considering the
e..ects o. inter2electronic repulsion and spin2or3it coupling, and this is e0ually true o.
ions7 Durthermore, 6e ha/e here the additional complication o. the crystal Leld7 That is,
the 9amiltonian operator .or the pro3lem is o. the .orm1
9

= 9

0
+ 9

er
+ 9

S"
+ 9

c.
in 6hich 9

0
represents the 4inetic energy o. the electrons on the central ion and
their attraction to the nucleus o. the ion, 9

er
is the inter2electronic repulsion, 9

S"
the
spin2or3it coupling and 9

c.
the crystal Leld7 As in the case o. the .ree atom 6here
there 6as no 9

c.
, 6e ha/e to decide the order in 6hich 6e apply terms 2, , and * to
correct 9

0
7 At
turns out that, o. the se/eral possi3ilities, only three are important in practice7
An the rare earth co1%ling scheme, 6here 9

S"
is large, 6e diagonalise the matrices o.
9

er
and 9

S"
3e.ore using 9

c.
7 Thus, in this case 6e determine the energy le/els o.
the
.ree ion as eactly as possi3le, 3e.ore considering the pertur3ation o. those le/els 3y the
crystal Leld7 !ro3lems o. this type are .e6 in chemistry and 6e shall not consider them
.urther here since the other t6o possi3ilities are much more important7
An the 0ea;+Celd co1%ling scheme, 9

c.
is applied as a pertur3ation to the terms o. the
.ree2ion 6hich result .rom 9

0
+
9

er
and the spin2or3it coupling, 9

S"
, is added
last7
An the strong+Celd co1%ling scheme the one2electron or3itals o. the central ion are
Lrst com3ined under the inOuence o. 9

c.
, and then 9

er
and 9

S"
are introduced, in
that
order7 Thus, in the t6o schemes 6hich are o. most interest to chemistry, the e..ect o.
spin2or3it coupling is introduced last7 This is reOected in our treatment here in that in
Sections -7,7# to -7,7* 6e Lrst study the e..ects o. 9

c.
, and 9

er
lea/ing the
introduction
o. 9

S"
until Section
-7,757
+

2
+1'1% T$e wea>9Bel/ s#$eme "or /
&
Fexample o"
'
6 in an o#ta$e/ral Bel/G
An the 6ea42Leld approach 6e Lrst determine the terms o. the .ree ion using the methods
in Chapter 57 We then calculate the e..ect o. the crystal Leld upon these terms and 6e are
usually most interested in the term o. highest multiplicity 3ecause, according to 9und,
this 6ill 3e the ground term 6ith the lo6est energy7 An the case o. the
,
D arising .rom
d
2
6e can 6or4 6ith the 5
S
=
# component o. the triplet .or 6hich the re0uired 6a/e
.unctions are (Appendi #0+1
|, , = | + 2
+
+#
+
!#,

2" {|G
2 2
!#"
G
2+#
!2" G
2+#
!#" G
2+2
!2" }
|, 2 = | + 2
+
0
+

|, # =
!2,5"
| +
#
+
0
+
+
!,,5"
| +
2
+

#
+

|, 0 = !2,

5" | + #
+
#
+
+ !#,

5" | + 2
+
2
+

|, # = !2,5" |0
+
#
+
+

!,,5" | + #
+
2
+

|, 2 = |0
+
2
+

|, , = | #
+
2
+

;ote that all ;ets on the right2hand sides o. the a3o/e e0uations are t6o2electron Slater
determinants (Appendi ?+ characterised 3y the m /alues o. the occupied d2or3itals7 A
superscript
+
sign indicates that the electron has m
s
= +
#
7 'ach determinant can 3e
epanded as a di..erence o. t6o or3ital products as has 3een illustrated a3o/e .or the
case o. | + 2
+
+#
+
7 The su3scripts on G are the l and m /alues 6hich characterise that
or3ital7
The calculation o. the matri elements o. 9

c.
is illustrated 6ith the eample o. the
element, , ,|9

c.
|, , in Bo -727
The complete matri is .ound to 3e1
9

c.
|, +, |, # |, , |, +# |, +2 |, 2 |, 0
, +,| , ,#0

#5 ,#0 0 0 0 0 0
, #|

#5 ,#0 ,#0 0 0 0 0 0
, ,| 0 0 , ,#0

#5 ,#0 0 0 0

,
+
#
|
0 0

#5 ,#0

,#0 0 0 0
, +2| 0 0 0 0 - ,#0 ,2 0
, 2| 0 0 0 0 ,2 - ,#0 0
, 0| 0 0 0 0 0 0 , ,5
The eigen/alues o. this matri are1
, H5, three.old degenerate1 group theoretical designation,
,
T
#
7
+ H5, three.old degenerate1 group theoretical designation,
,
T
2
7
+
? H5, singly degenerate1 group theoretical designation,
,
A
2
7
At is use.ul to note here that the presence o. three o..2diagonal elements in the a3o/e
matri means that the three pairs o.
,
D 3asis states |, +, and |, # |, +2 and
|, 2 |, +# and |, , are mied 3y the Leld in proportions 6hich depend upon the
/alue o. 7 "ne 3asis state, the |, 0 6hich is a component o. the
,
T
#
, is not mied


3y the Leld and 6e shall Lnd this use.ul 6hen 6e ta4e account, as 6e do no6, o. the
presence o. another state o.
,
T
#
symmetry .ormed 3y the d or3itals, the
,
!7
+1'1& T$e wea>9Bel/ s#$eme "or /
&
Fin#l;sion o"
'
!G
The electron conLguration d
2
gi/es rise to t6o sets o. triplet states,
,
! and
,
D, and
in accordance 6ith 9undGs rules, E(
,
!+ is greater than E(
,
D+7 9o6e/er, the energy
gap 3et6een the t6o is not, in general, so large that 6e can ignore the
,
! le/elsP
especially in the interpretation o. spectra7 There.ore, 6e must no6 eamine the e..ect
o. the octa2
hedral crystal Leld on the
,
! state7 =sing the same notation as a3o/e, the three
|
L 5
L

components o. the state ha/ing 5
S
=
#.0 may 3e 6ritten1
|# # = !2,5" |2
+
#
+

!,,5" |#
+
0
+

|# 0 = !2,

5" |2
+
2
+
!#,

5" |#
+
#
+

|# # = !2,5" |#
+
2
+

!,,5" |0
+
#
+
.
The , , matri o. 9

c.
in this 3asis can 3e constructed in eactly the same manner as
that used a3o/e .or
,
D7 9o6e/er, 6e Lnd only three e0ual diagonal elements o. , 6hich
6e neglect, and no elements containing appear7 This should come as no surprise7 A
! state has the same electron distri3ution as a p or3ital and i. 6e thin4 o. the three real
p or3itals (Chapter 5+ it is clear that each one points in an identical manner to t6o o.
the si charges .orming the octahedral Leld7 The triple degeneracy o. p or3itals or a !
state is not li.ted 3y an octahedral Leld, as the symmetry designation
,
T
#
conLrms7 But
there are matri elements o. 9

c.
3et6een components o. the
,
! and
,
D states and so
our
- - matri .or the latter should 3e etended to #0 #0 in order to include the .ormer7
Dortunately, this is unnecessary7 A. 6e re0uire only the energies o. the mied
,
! and
,
D
states, 6e can ma4e use o. the .acts that the Leld does not mi the |, 0 component o.
the
,
D 6ith any other component o. that state and the |#,0(
,
!+ interacts solely 6ith the
|
, 0

component o. the
,
D state7 There.ore, 6e need to e/aluate only the matri element

,,0(
,
D+
|
9

c.
|
#,0 (
,
!+
7
=sing the 6ell2tried methods 6e Lnd1
9

c.
|, 0!
,
9 " |# 0!
,
P "
, 0!
,
9 "| , ,5 +2 ,5

# 0!
,
P "
| +
2 ,5 0
+

6here is the com3ination o. electron repulsion integrals 6hich are responsi3le .or the
di..erence in energy o. the
,
! and
,
D states (see Bo -7,+7 At is interesting to determine
the
eigen/alues o. this matri at the 6ea42Leld etreme, = 0, and the strong2Leld etreme,
7 When = 0 the eigen/alues are 0 and , i7e7 the separation o. the t6o states is,
as 6e 6ould epect, the same as it 6ould 3e in the .ree gaseous ion7 When 6e can
neglect and Lnd that the eigen/alues are * H5 and + H57 We can conLrm that these
are the epected strong2Leld eigen/alues 3y noting that, in an octahedral crystal Leld, the
energies o. the L/e d or3itals split into t6o groups, e
g
at + , ,5 and t
2g
at 2 H57
;eglecting the common contri3ution to the energy, , 6e see that the lo6est possi3le
energy o. our d
2
system in a strong crystal Leld occurs 6hen 3oth electrons occupy a
'
n
e
r
g
y

(
a
r
3
i
t
r
a
r
y

u
n
i
t
s
+
'
n
e
r
g
y


(
#
0
,

c
m

#
+
A
= 0
= 0
,
! #070
-75
570
,
2
(e
g
+
#
(e
g
+
#
275
,
D 070
275
570
070 075 #70
,
T
#
(!+
,
T
2
,
T
#
(D+
075
(t
2g
+
#
(e
g
+
#
(t
2g
+
#
(t
2g
+
#
070
Wea4 .ield
/ /
Strong .ield
6ig;re +1( Correlation diagram o. d
2
in an octahedral Leld
50
,
A
2
*0
,
T
#
(
,
!+
,0
,
T
2
20
#0
,
T
#
(
,
D+
0
0 5 #0 #5 20 25
Crystal .ield (+ (#0
,
cm
#
+
6ig;re +1) An "rgel or Tana3e2Sugano diagram .or d
2
di..erent t
2g
or3ital 6ith parallel spins, gi/ing E{!t
2g
"
#
!t

2g
"
#
} = * H57 A. 6e ha/e one
electron in a t
2g
and one in an e
g
the energy is E{!t
2g
"
#
!e
g
"
#
} = 2 ,5 + , ,5 = + ,57 We
should also note that E{!e
g
"
#
!e

g
"
#
} = +? ,57 We no6 ha/e the theoretical analysis
re0uired to determine the triplet energy le/els o. a d
2
ion in an octahedral crystal Leld
o. any magnitude and .or any /alue o. the
,
!
,
D splitting7 The results are illustrated in
Digures -7* and -75 6hich sho6, in di..erent 6ays, ho6 the energies depend on and 7
+1'1' T$e /
&
energ0 leAels "or wea>< strong an/ interme/iate
o#ta$e/ral Bel/s
Dirst, 6e summarise our epressions .or the energies7
An the intermediate region, the energies o. the
,
D states 6hich do not mi 6ith
,
! are1
E!
,
A
2
1
,
D" = +? ,5 and E!
,
T
2
1
,
D" = + ,5
The energies o. the interacting
,
! and
,
D states, o3tained 3y diagonalising the
interac2 tion matri a3o/e, are1
# # 2 2
#
E!
,
T
#
1
,
!"
= +
!

, ,5"
+ {
!Z, ,5\

"
+
, ,5
+
!2 ,5"
}
2
2 *
# # 2 2
#
E!
,
T
#
1
,
D"
= +
!

, ,5"
{
!Z, ,5\

"
+
, ,5
+
!2 ,5"
}
2
2 *
So that in the strong2 and 6ea42Leld limits 6e ha/e1
Wea42Leld limit Strong2Leld limit
= 0 = 0 = 0 = 0
E!
,
!" = E{!e
g
"
#
!e
g

"
#
} = +? ,5
E
{
!e
g
"
#
!t
2g
"
#
} = +
,5
E!
,
D"
=
0 E
{
!t
2g
"
#
!t
2g

"
#
} =
* ,5
An Digure -7* the energies o. the .our d
2
states, calculated using the epressions a3o/e,
are plotted against , in the le.t2hand hal. o. the diagram and against , in the right2
hand hal.7 The .ar le.t is the 6ea42Leld limit 6here = 0, 6hile the .ar right corresponds
to the strong2Leld limit 6here = 0, and the Lgure represents all possi3le relati/e /alues
#
o. the t6o parameters7 The energies ha/e 3een di/ided 3y 0.# {#.0 + H
2
} 2
on the le.t and
#
3y 0.2
{
#.0
+
!#,H "
2
} 2
on the right, 6here H
=
2 , 7 The .actors 0.# and 0.2 are
chosen to ma4e the total span o. energy le/els at 3oth etremes o. the diagram the same7
The .actors in parentheses ensure that le/els meet at = 7 Lo6
5
has measured the
electronic spectrum o. 8
,
+
ions (conLguration1 Ar ,d
2
+ in an aluminium oide host and
Lnds prominent 3ands at #- *00, 25 200 and ,* 500 cm

#
7 This is a d
2
ion
octahedrally
coordinated 3y oide ions and represents eperimental data 6hich may 3e interpreted
using Digure -7*7
We proceed as .ollo6s7 The energies o. the three 3ands o3ser/ed 3y Lo6 are in the
approimate ratios # 1 #75 1 2 and 6e there.ore see4 a position on the horiKontal ais
o. Digure -7* 6here the energy gaps 3et6een the lo6est le/el and the three a3o/e it
are
in these ratios7 We Lnd it on the strong2Leld side o. the diagram 6here , 0.557
This assigns the spectrum and gi/es us the ratio o. to 7 By noting that the energy
gap 3et6een the
,
A
2
and
,
T
2
states is , 6e Lnd their approimate a3solute /alues to
3e #- #00 and $*00 cm

#
7 The 6ord a%%roximate is used .or three reasons7
Dirstly, since 6e ha/e three energy di..erences and t6o un4no6ns, the pro3lem is o/er2
determined and slightly di..erent /alues o. the parameters 6ould 3e o3tained 3y using
the data in a di..erent 6ay7 Secondly, the o3ser/ed 3ands are 3roadened 3y /i3rational
e..ects and the position o. the pure electronic transition cannot 3e determined to 3etter
than

500 cm

#
7 Thirdly, and most importantly, this simple CD model does not @usti.y
more eact analysisP the agreement o. theory 6ith eperiment is already 0uite remar4a3le
and the ma@or aim o. assigning the spectrum has 3een achie/ed7
A second diagrammatic 6ay o. analysing the spectrum o. a d
2
ion in an octahedral
en/ironment is sho6n in Digure -757 <iagrams o. this type 6ere Lrst deri/ed 3y Tana3e
and Sugano and 3y "rgel in #$5*H57 Digure -75 is a reproduction o. part o. the Tana3e
and Sugano diagram .or d
2
7 The e..ect upon the triplet state energies o. increasing at a
constant /alue o. ($500 cm

#
in this Lgure+ is sho6n in 6a/e num3er units7 The energy
o. the
,
T
#
!
,
D" ground state is su3tracted .rom each o. the .our energy le/els7 At
there.ore appears in the diagram as a horiKontal line o. Kero energy so that the energy
gaps to the other three states are 0uantitati/ely represented 3y their /ertical heights a3o/e
this ground state line7 A good approimation to the eperimental data, and there.ore an
assignment
o. the spectrum, is o3tained 6here

#% ,00 cm

#
7 The di..erence in the /alue o.
.ound .rom the t6o diagrams should not 3e thought signiLcant7 Since 3oth are 3ased on
eactly the same theoretical analysis, the same /alues o. the t6o parameters, and ,
could 3e deduced .rom eitherP 3ut any attempt to 3ring the results closer together 6ould
3e 0uite un@ustiLed 3y the simple model and the uncertainties inherent in the assignment
o. precise energies to 3road eperimental 3ands7
Tana3e and Sugano reported diagrams o. the a3o/e type .or d
2
to d
%
ions and repro2
ductions o. them can 3e .ound in numerous 3oo4s7 Both aes are usually graduated in
units o. :acahGs B parameter, a measure o. the electron repulsion in the ion7 Dor the d
2
case, .or eample, B = ,#57 An this 6ay a single diagram can 3e made /alid .or all ions
ha/ing the same num3er o. d electrons, in contrast to Digure -75 6hich applies only to a
d
2
ion 6ith = $500 cm

#
7
A .e6 remar4s concerning the relati/e merits o. Digures -7* and -75 are in order7 At
Lrst glance, the energy2le/el plots o. Digure -75 appear to 3e straight lines, and the .act
that the energies o.
,
A
2
and
,
T
2
depend only on suggests that they should indeed
3e linear7 The energies o. the t6o
,
T
#
states depend on as 6ell as and are
there.ore epected to 3e cur/es7 9o6e/er, 3ecause 6e ha/e made
,
T
#
(D+ a 3ase line its
cur/ature has 3een superimposed upon the plots o. the other three energies7 But the
cur/ature is slight7 Core important is the .act that Digure -75 sho6s energies as a
.unction o. 3ut 6ith a Led, pre2selected /alue o. and there.ore applies .or that
/alue o. only7 This o3@ection does not apply to Tana3e2Sugano diagrams in general,
nor to Digure -7* in 6hich all possi3le relati/e /alues o. and are sho6n in the one
Lgure7 The dra63ac4 is that only relative /alues are represented and the diagram conceals
the linear dependence o. some states on 7
+1'1( T$e strong9Bel/ s#$eme "or /
&
in an o#ta$e/ral Bel/
The po6er and ready a/aila3ility o. digital computers ha/e made it easy to calculate the
energy le/els o. a d
2
ion in an octahedral Leld .or any com3ination o. parameters, e/en
6hen the singlet states are included7 At 6as not al6ays so7 Durthermore, 6hen under2
standing as 6ell as a 0uantitati/e analysis is sought, a thought.ul, alge3raic approach to a
pro3lem has much to recommend it and so 6e no6 approach the pro3lem .rom the strong2
Leld end7 An the strong2Leld approimation to the d
2
pro3lem 6e Lrst diagonalise 9

c.
and o3tain the real d or3itals 6ith energies + , ,5 and 2 ,5, as in Section -727
A. 6e then .ocus our attention on the states o. highest multiplicity, i7e7 states in 6hich
the t6o d electrons occupy di..erent or3itals 6ith their spins parallel, 6e see that 6e can
.orm the .ollo6ing conLgurations1
!t
2g
"
#
!t
2g

"
#
E = 2 ,5 2 ,5 = * ,5 E!
,
T
#
1 t
2g
2
"
!t
2g
"
#
!e
g
"
#
E = 2 ,5 + , ,5 = + ,5 E!
,
T
#
1 t
2g
e
g
" and E!
,
T
2
"
!e
g
"
#
!e
g

"
#
E = , ,5 + , ,5 = +? ,5 E!
,
A
2
"
2
2
The uni.orm rise in energy o. 2 has 3een neglected and the t6o states o. T
#
symmetry
are distinguished 3y the electron conLgurations .rom 6hich they originate7 ;ote that t6o
distinct states,
,
T
#
and
,
T
2
, arise .rom the conLguration !t
2g
"
#
!e
g
"
#
7 These states also
di..er in energy 6hen electron repulsion is included due to the di..erent spatial
distri3utions o.
the K
2
and
2

y
2
d2or3ital 6a/e .unctions (see Bo -7,+7
We no6 ha/e to introduce the pertur3ation o. the inter2electronic repulsion represented
3y 9

er
7 This 6ill change the energies o. the electronic states and 6e can calculate
this
change 3y epressing each conLguration as a Slater determinant in 6hich the real d
or3itals are epressed in terms o. the G
lm
7 The calculation is 0uite straight.or6ard 3ut
tedious and 6e 6ill not do it here7 At is 6ell descri3ed 3y Ballhausen7
#
We Lnd that the
electron repulsion raises the energy o. each state as sho6n in the matri 3elo67 Since
6e are only interested in energy di..erences, a constant term (:acahGs A+ 6hich arises in
each diagonal has 3een omitted7 Anterelectronic repulsion may also cause states to mi,
a phenomenon 4no6n as conLguration interaction7 9o6e/er, group theoretical principles
tell us that states o. di..erent symmetries cannot 3e mied 3y an operator li4e 9

er
,
6hich
has the .ull symmetry o. the system, and 6e there.ore epect that there 6ill 3e miing
only 3et6een the t6o states o. T
#
symmetry7 The complete energy matri, including the
crystal Leld 3ut 6ith 2 + A omitted .rom each diagonal element, is1
9

er
E!
,
T
#
1 t
2g
2
" E!
,
T
#
1 t
2g
e
g
" E!
,
T
2
" E!
,
A
2
"
E!
,
T
#
1 t
2g
2
"
* ,5 ,, 2 ,5 0 0
E!
,
T
#
1 t
2g
e
g
"
2 ,5 + ,5 + * ,#5
0 0
E!
,
T
2
" 0 0
+ ,5 % ,#5
0
E!
,
A
2
" 0 0 0
+? ,5 % ,#5
The eigen/alues o. the 2 2
,
T
#
matri are , ,#0 ,,0
#
{
2
+
2
+ ? ,
#
5
} 2
7 We can chec4 this result 3y noting that at Kero electron repulsion (
=
0+ the
,
T
#
eigen/alues are * ,5 and + ,5, 6hile at Kero Leld ( = 0+ their energy separation
is 7 These are the correct limiting results7 The s0uare root in the a3o/e energies ma4es
their use in assigning spectra and determining the /alues o. the parameters and a
little di.Lcult7 But in the strong Leld regime 6here terms in the energy 6hich
in/ol/e ! , "
2
or higher po6ers may 3e neglected and 6e can approimate the s0uare
root as .ollo6s1
# #
{

2
+

2
+
? ,5
} 2 =

{
#
+
! , "
2
+
? ,5
} 2
#


{
#
+
? ,5
} 2

{
#
+
#

? ,5
} =

+
, ,5
With this approimation E!
,
T
#
1 t
2g
2
" = * ,5 + ,5 and the energy di..erences, in
ascending order, 6hich might 3e compared 6ith eperimental data, are1
E!
,
T
2
" E!
,
T
#
1 t
2g
2
" = ,5
E!
,
T
#
1 t
2g
e
g
" E!
,
T
#
1 t
2g
2
" = + , ,5
E!
,
A
2
" E!
,
T
#
1 t
2g
2
" = 2 ,5.
Aleander and Gray
?
ha/e reported 3ands at 22 -00 cm

#
and 2- 200 cm

#
in the spec2
trum o. the comple, ,d
2
ion Z8(C;+
?
\
,

7 A. 6e assign the Lrst o. these 3ands to the


'
n
e
r
g
y

(
#
0
,

c
m

#
+
E!
,
T
#
1 t
2g
2
" E!
,
T
2
" transition and the second to the E!
,
T
#
1 t
2g
2
" E!
,
T
#
1 t
2g
e
g
"
6e readily Lnd 2, %00 cm

#
and 5?00 cm

#
7 The large /alue o. , sho6s
that 6e really are in the strong2Leld regime and @ustiLes the a3o/e neglect o. ! , "
2
and
higher po6ers7 With these /alues o. and 6e predict that the E!
,
T
#
1 t
2g
2
" E!
,
A
2
"
3and should lie at a3out *? 500 cm

#
6here it is hidden under much stronger 3ands due
to other electronic transitions7
+1'1) Spin9or?it #o;pling
The Lnal inOuence upon energy le/els is that o. spin2or3it coupling 6hich, .or the tran2
sition metals o. the Lrst series, is much smaller than the crystal Leld or the electron
repulsion7 At 3ecomes increasingly important as 6e descend the periodic ta3le and espe2
cially 6hen 6e encounter the rare earths7 As an illustration 6e consider the e..ect o.
increasing spin2or3it coupling on the conLguration d
2
in a strong crystal Leld (Digure -7?+7
"n the le.t the .our triplet energy le/els are plotted7 The matri o. all *5 possi3le d
2
states
has 3een diagonalised 6ith = 5?#0, = 2, %00 and the spin2or3it coupling constant,
V
d
= 0 2000 cm

#
7 These /alues o. the parameters 6ere chosen so as to reproduce the
spectrum o. Z8(C;+
?
\
,

discussed a3o/e at lo6 /alues o. V
d
7 The energy o.
,
T
#
!
,
D"
6hen
V
d
= 0 has 3een set to Kero and, in order to include all #, distinct le/els in one diagram,
#$ 000, 20 000 and ,- 000 cm

#
ha/e 3een su3tracted .rom the energies o. the
,
T
2
,
,
T
#
and
,
A
2
states respecti/ely7 All
,
T le/els 3eha/e 0ualitati/ely as i. they 6ere
,
!, that
is they gi/e rise to states ha/ing Q != L + S" /alues o. 2, # and 0 .or non2Kero V
d
, and
the
52.old degeneracy o. the Lrst is li.ted .urther 3y the crystal Leld7 The de/elopment o. the
le/els as V
d
is increased .rom Kero to 2000 cm

#
is sho6n 6ith the Q /alues, and degen2
eracies (2Q + #+ on the right7 ;ote that at lo6 /alues o. V
d
the L/e2.old degeneracy o.
the states 6ith Q = 2 is scarcely li.ted and in this range the le/els in each group o3ey an
approimate Landeb inter/al rule, i7e7 E!Q = 2" E!Q = #" 2{E!Q = #" E!Q = 0"}7
An order to assess the e..ect o. spin2or3it coupling on electronic spectra 6e Lrst note
that the ranges o. the eperimentally determined /alues o. V
nd
are 50 I %50, 200 I
#$00 and ,00 I 5000 cm

#
.or n = ,, * and 5 respecti/ely
*
6hilst eperimental 3and 6idths
#070
,
A
2
I ,-70
(e+
#
(e+
#
,
J = #
2
#070
%70
,
T
#
(
,
!+ I 2070
,
J = 2
%70
?70
*70
270
070
270
(t
2
+
#
(e+
#
,
T
2
(
,
D+ I #$70
(t
2
+
#
(e+
#
,
T
#
(
,
D+
(t
2
+
#
(t
2
+
#
070 075 #70
,
J = #
#
J = 0
2
J = 2
,
,
J = #
#
J = 0
#
J = 0
,
J = #
,
J = 2
2
#75 270
?70
*70
270
070
270
Spin2or3it coupling constant K
d
(#0
,
cm
#
+
6ig;re +1* The e..ect o. spin2or3it coupling on the strong2Leld triplet states o. d
2
typically lie 3et6een #000 and *000 cm

#
7 Thus, the splittings in Digure -7? attain the
order o. magnitude o. typical 3and6idths only on the right2hand side o. the diagram
6here V
d
= 2000 cm

#
7 Such /alues o. V
d
are not .ound until the end o. the second
transition metal series and in the third7 The result is that it is rare to see e/idence o.
spin2or3it coupling in the .orm o. 3and splittings in electronic spectra7 By miing states
o. di..erent multiplicity, spin2or3it coupling also causes 3rea4do6n o. the strict S = 0
selection rule (see Section 57##+ 3ut this e..ect also re0uires that V
d
ha/e a su3stantial
/alue and spectral 3ands made allo6ed in this manner are rarely o3ser/ed 6ith light
transition metals7 9o6e/er, Aleander and Gray
?
o3ser/ed t6o such 3ands,
,
T
#g

#
T
2g
at #* ?00 cm

#
and
,
T
#g

#
T
#g
at #$ 200 cm

#
, in their spectrum o. >
,
8(C;+
?
7
Dor 8
,
+
V
d
%?0 cm

#
7
Thus .ar in our account o. the theory o. the electronic structure and 3onding in
transition2metal complees 6e ha/e gi/en a .airly detailed analysis o. d
2
systems7 An
a non2specialised /olume such as this, space does not permit a similar treatment o. d
,
to
d
#0
.or 6hich 6e must re.er the reader to the 3i3liography7
#*
We ha/e 3een dra6n into
a consideration o. electronic spectra 3ecause spectral data pro/ide the most direct 6ay o.
determining and , the essential parameters o. the CD model7 ;o account o. the theory
o. the transition2metal ions 6ould 3e complete 6ithout some re.erence to their electronic
spectroscopy7 But this is a /ast and complicated su3@ect 6hich is 6ell treated in a num3er
o. specialist /olumes
*-
and here 6e can only dra6 attention to a .e6 signiLcant points7
+1( THE E5ECTR2NIC S!ECTR2SC2!Y
26 TRANSITI2N9META5 C2M!5EDES
Thus .ar 6e ha/e compared the positions o. calculated and o3ser/ed electronic transitions
6ithout as4ing 6hether or not those transitions 6ere su.Lciently intense to 3e seen7 Since
6e ha/e 3een concerned eclusi/ely 6ith d electrons, the states in/ol/ed must all 3e o.
e/en parity and the transitions, all d d, 3et6een states o. the same parity7 Spectroscopic
selection rules are discussed in detail in Sections 57##, %7* and %75, so it su.Lces here to
say that transitions 3et6een states o. the same parity are strictly .or3iddenP the Laporte
rule7 The .act that these d d 3ands, though rather 6ea4, are indeed o3ser/ed is due to
the loss o. parity 6hich can arise in either a static or a dynamic manner7 A. the ligand
en/ironment is not strictly octahedral, e7g7 3ecause o. a slight static distortion, then the
centre o. symmetry o. the comple as a 6hole may 3e lost and 6ith it the deLniti/e
e/en parity o. the d or3itals and states7 A d d transition may then 3ecome 6ea4ly
allo6ed, .re0uently 3ecause the lo6ered symmetry allo6s p and d or3itals to mi7 This
is particularly true o. tetrahedral complees7 The tetrahedron has no centre o. symmetry
and the d d transitions o. tetrahedral complees are in/aria3ly more intense than those
o. their octahedral counterparts7 The loss o. symmetry need not 3e permanent and staticP
/i3rations can ha/e the same e..ect o. ma4ing a transition partially allo6ed7
The CD model is concerned solely 6ith the energies o. the d2electron states 3ut the
intense colours o. many transition2metal complees, e7g7 the purple colour o. ZCn"
*
\

and
the 3lood red o. ZDe(C;S+
?
\
,

, arise not .rom d d transitions, 6hich as 6e ha/e seen


a3o/e are normally /ery 6ea4, 3ut .rom charge+transfer transitions in 6hich electrons
are trans.erred .rom the ligands to the metal (LCCT+7 ZDe(2,2

23ipyridine+
,
\
2
+
sho6s a
strong a3sorption at 522 nm due to the re/erse process, a metal2to2ligand charge trans.er
The Cagnetism o. Transition2Cetal Complees #$-
(CLCT+7 Transitions o. this type are .urther e/idence o. co/alency and re0uire a molecular
or3ital treatment .or their 0uantitati/e understanding7
Apart .rom in Section -7,75, 6e ha/e re.erred only to transitions 3et6een states o.
the same multiplicity, triplet states in the case o. d
2
7 d d transitions 6hich in/ol/e a
change o. multiplicity, triplet to singlet in the case o. d
2
, are dou3ly .or3idden and are
/ery 6ea4 indeed7 But as spin2or3it coupling gro6s in the *d and 5d series o. metals,
and especially in the rare earths, nominally spin2.or3idden transitions gain in intensity
3ecause o. the loss o. a clearly deLned multiplicity .or each state7 The multiplicity o.
the ground state o. a transition2metal comple is not only important .or the electronic
spectroscopy o. the compound, there are other interesting conse0uences, some o. 6hich
6e eplore in the net t6o sections7
+1) !AIRIN ENERIESK 5249S!IN AN3 HIH9S!IN C2M!5EDES
Consider the au.3au principle as applied to a d
*
comple in a strong octahedral Leld7
Dollo6ing 9undGs rules, the Lrst three electrons 6ill 3e placed in the triply degenerate
t
2g
or3itals 6ith their spins parallel7 An placing the .ourth electron 6e ha/e a choice
3et6een dou3le occupation o. a t
2g
or3ital, gi/ing a triplet state, or the use o. an empty
e
g
or3ital gi/ing a 0uintet7 The actual or3ital occupation 6ill 3e that o. lo6er energy
6hich depends upon the relati/e magnitudes o. the interelectronic repulsion in a dou3ly
occupied t
2g
or3ital and the energy gap, , 3et6een the t
2g
and e
g
or3itals7 Calculation
sho6s that1
e
g

t
2g

'nergy
5
'
=
?A

2#B
+
'nergy
,
T
#
=
?A

#5B
+
5C
An these e0uations the electron repulsion energy is 6ritten in terms o. :acah parameters,
A, B and C
*
(Bo -7,+ and 6e do not re0uire to del/e into the eact .orm o. these integrals
to see that 6hen = ?B + 5C the energies o. the t6o states are e0ual7 Similar e0ualities
arise in the d
5
, d
?
and d
-
cases so that a large crystal2Leld splitting causes electron spins
to pair 6hilst small /alues o. lead to the maimum num3er o. unpaired spins7 The
corresponding complees are re.erred to as lo0+s%in and high+s%in respecti/ely7 Though
the conse0uences o. the t6o possi3ilities .or electron pairing can 3e detected in the spectra
o. the comple and in many o. its other physical and chemical properties, the e..ect is
most mar4ed in its magnetic 3eha/iour 6hich is largely determined 3y the num3er o.
unpaired electrons7
+1* THE MANETISM 26 TRANSITI2N9META5 C2M!5EDES
The .ollo6ing .ormula .or the magnetic moment (T+ o. a molecule in Bohr magnetons is
discussed in Section #2721
#
T
total
=
Z
{
L!L
+
#"
} +
*
{
S!S
+
#"
}
\
2
T
B
At is appropriate .or situations in 6hich the multiplet splittings that result .rom spin2
or3it coupling are small compared 6ith ;- and should there.ore 3e applica3le to the
#$% Transition2Cetal Complees
2 # # #7-, ,700
f
2 # # #7-, ,700
f
, - , ,7%- 5720
f
, % 2 27%, *7*- 2.% ,.5
2 $ # #7-, ,700 #.- 2.2
Ti
,+ #
2
8
*
+
8
,
+
Cr
,
+
Cr
2
+
#
#
,
2
Cn
2
+
5
De
,
+
5
2
transition2metal ions .rom Ti
,
+
to Cu
2
+
.or 6hich the spin2or3it coupling constant, V
d
, is
small7 L and S are the total or3ital and spin angular momenta respecti/ely7 An Ta3le -7,
the a3o/e .ormula is used to calculate the magnetic moments o. the .ree transition2metal
ions o. the Lrst transition series and the results are compared 6ith the measured moments
.or the octahedrally co2ordinated ions in their high2spin states7 The T
S
(spin2only+ /alues
6ere calculated 3y setting L = 07 The conLgurations mar4ed f are those .or 6hich there
can 3e an or3ital contri3ution to the magnetic moment (see 3elo6+ n = num3er o. d
electrons, n

=
num3er unpaired7
Comparison o. the theoretical and eperimental data in Ta3le -7, re/eals that, in many
cases, the eperimental magnetic moment is 0uite close to the spin2only /alue, i7e7 the
electronic or3ital angular momentum appears to contri3ute /ery little to the total magnetic
moment o. a ,d
n
transition2metal ion7 This has the important, and particularly use.ul, con2
se0uence that T
ep .
gi/es a /ery direct indication o. the num3er o. unpaired electrons7 The
reason .or the small contri3ution .rom the or3ital motion o. the electrons is that this has
3een 71enched 3y the interaction o. the metal d2electrons 6ith the ligands7 An our model
this interaction is purely electrostatic, 3ut the .act that the 0uenching is in many cases so
complete strongly suggests that there is co/alent 3onding 3et6een ligand and metal7 The
latter pro/ides an e/en 3etter 0uenching mechanism since it pre/ents the electrons .rom
circulating the metal nucleus 3y loc4ing them into localised chemical 3onds7
Though the lac4 o. an or3ital contri3ution to the magnetic moment is readily 0ual2
itati/ely understanda3le, it is o. interest to en0uire 6hether 6e can place the concept
o. 0uenching on a Lrmer theoretical 3asis in order to understand 6hy, in some cases at
least, signiLcant or3ital contri3utions to the magnetic moment remain7 An pursuit o. this
o3@ecti/e 6e Lrst recall the matri o. the L/e d or3itals in an octahedral crystal Leld
Ta?le +1' Calculated magnetic moments, in Bohr magnetons, o. the ground
states o. some .ree transition2metal ions and the eperimental magnetic moments
.or the octahedrally co2ordinated ions in their high2spin conLgurations
Aon S L n n

T
S
T
total
T
ep
#.- #.%
2
#.-

#.%
, 2 2 27%, *7*- 2.?

2.%
f
2
, , , ,7%- 5720 ,.-

,.$
2 * * *7$0 57*% *.- *.$
Cn
,
+
2 2 * * *7$0 57*% *.$

5.0
2
0 5 5 57$2 57$2 5.?

?.#
2
0 5 5 57$2 57$2 5.-

?.0
De
2
+
2 2 ? * *7$0 57*% 5.# 5.5
f
Co
,
+
2 2 ? * *7$0 57*% ca7 57*
f
Co
2
+
,
2
;i
2
+
#
Cu
2
+
#
*.# 5.2
f
The conLgurations mar4ed f are those .or 6hich there can 3e an or3ital contri3ution to
the magnetic moment, see tet7 n = num3er o. d electrons, n

= num3er unpaired7
97L7 SchlaM.er and G7 Gliemann, /asic Princi%les of Ligand 9ield -heory7 #$?$, John
Wiley & Sons LtdP reprinted 6ith permission7
(Section -72+ and the remar4s .ollo6ing it7 The t6o d or3itals, ha/ing m /alues o. +2
and 2, 6ere .ound to ha/e eactly the same diagonal matri element ( + ,?+ and
to 3e connected, and hence mied, 3y an o..2diagonal matri element o. 5 ,?7 Since
the diagonal elements are e0ual, the resulting mied 6a/e .unctions, d
y
and d

y
2 , 6ill
each contain e0ual parts o. m = +2 and m = 2 and 6ill there.ore ha/e no K2component
o. or3ital angular momentum7 Since there are no other o..2diagonal matri elements,
the remaining three d or3itals 6ill retain their K2components o. angular momentum o.

#h,2( and 07 An an octahedral Leld, the description o. these or3itals as d


K
, d
yK
and
d
K
2 rather than as d
+#
, d
#
and d
0
is a matter o. choice, not o. necessity7 There.ore,
6hen a magnetic Leld is applied along the K2direction the d
#
6ill 3e slightly lo6er in
energy than the d
+#
, 3ecause o. the Leld produced 3y the or3iting electron, and i. the
conLguration is such that it is possi3le to place more electrons in d
#
than in d
+#
an
or3ital contri3ution to the total magnetic moment o. the material may result7 But note
that this potential or3ital moment can still 3e 0uenched 3y .orces not considered in our
simple electrostatic interaction matri7 Adenti.ying the t6o groups o. degenerate d or3itals
in the octahedral Leld 3y their group2theoretical sym3ols, the conLgurations 6hich can
mani.est an or3ital contri3ution to the magnetic moment are, .or high spin, i7e7 minimum
possi3le electron pairing1 (t
2g
+
#
, (t
2g
+
2
, (t
2g
+
*
(e
g
+
2
and (t
2g
+
5
(e
g
+
2
7 These conLgurations
are mar4ed f in Ta3le -7,7 An the lo6 spin conLgurations 6ith maimum spin pairing
the conLgurations (t
2g
+
*
and (t
2g
+
5
may contri3ute or3ital moments7 When 6e compare
the high2spin predictions 6ith the a3o/e ta3le 6e see that the ions 6ith si and se/en d
elec2 trons are indeed those 6here the highest eperimental moments match T
total
most
closely7 The minimal or3ital contri3utions to the ions 6ith one or t6o d electrons are
thought to 3e due to de/iations o. the complees .rom eact octahedral geometry7 This
may 3e a result o. .orces in the crystal lattice (all the measurements in Ta3le -7, 6ere
made on solids+ or they may 3e due to a Jahn2Teller e..ect, the origin o. 6hich space
does not allo6 us to pursue .urther here7 An either case, a small distortion lin4s the d
+
#
and d

#
or3itals 6ith a small o..2diagonal matri element and causes them to mi .orming d
K
and
d
yK
, 6here3y the K2component o. their or3ital angular momentum is lost7
As a last 6ord on the comple su3@ect o. or3ital contri3utions to magnetic moment
6e might note that, i. spin2or3it coupling is signiLcant, in conLgurations ha/ing less than
L/e electrons the spin and or3ital angular momenta are antiparallel in the state o. lo6est
energy so the or3ital contri3ution has to 3e su3tracted .rom the spin contri3ution7 The
re/erse is the case 6here the num3er o. d electrons is greater than L/e7
+1+ C2VA5ENCY AN3 THE 5IAN3 6IE53 THE2RY
As early as #$,5, 8an 8lec4 recognised that any 6idely applica3le theory o. transition2
metal complees 6ould ha/e to include the e..ects o. co/alent interaction 3et6een metal
and ligand, e/en though compelling eperimental e/idence .or it 6as una/aila3le at that
time7 An the #$50s, ho6e/er, Lrstly electron paramagnetic resonance ('!:+ and then
nuclear magnetic resonance (;C:+ measurements le.t no room .or dou3t and pro/ided
0uantitati/e e/idence7 The essential nature o. the e/idence is easy to eplain7 An the case
o. '!: spectroscopy,
%
6e measure the a3sorption o. radiation (in the micro6a/e region+
3y one or more unpaired electrons in a magnetic Leld 6here the energies o. electrons
# #
ha/ing m
s
= +
2
and m
s
=
2
are di..erent7 Apart .rom the magnetic Leld imposed 3y
the spectrometer, the electron sees other Lelds, in particular the Lelds due to the magnetic
nuclei (Chapter #0+, 6hich it /isits as it ma4es its peregrinations through the molecule7
These Lelds cause splittings, 4no6n as Cne str1ct1re, in the spectra and the magnitude o.
a particular splitting is proportional to the product o. the nuclear magnetic moment and
the pro3a3ility that the unpaired electron 6ill 3e .ound at that particular nucleus7
]
An this
6ay the interaction o. unpaired electrons .rom the Cn
2
+
ion 6ith D

ions in CnD
2
6as
o3ser/ed and measuredP to mention @ust one o. many similar eperiments7 Clearly, such a
hyperLne interaction is only possi3le i. there is miing o. metal and ligand atomic or3itals
to .orm molecular or3itals, i7e7 co/alency7 The ;C: e/idence is similarly direct and 6ill
not 3e discussed here7 Thus, co/alency cannot 3e denied, 3ut the great success o. the
simple CD theory also leads us to epect that there 6ill 3e important similarities 3et6een
the results o. an C" theory o. transition2metal complees and those o. the crystal Leld,
and indeed there are7
We can illustrate this point 3y applying the C" theory, in linear com3ination o.
atomic or3itals (LCA"+ .orm, to a simple, hypothetical, octahedral comple, C9
?
, in
6hich the d2or3itals o. the central metal ion .orm co/alent 3onds 6ith the #s or3itals o.
si surrounding hydrogen atoms placed e0ually distant .rom the metal atom at , y
and K (Digure -7-+7
"ur calculation 6ill use a /ery simple C" theory, 0uite li4e the 9uM c4el procedure
(Section #27#+ 3ut, 3ecause the interactions 3et6een the metal ,d or3itals and the sur2
rounding hydrogen #s or3itals, $
i
, are not all e0ual, 6e shall Lnd it necessary to use the
,d | #s o/erlap to estimate the 3onding 3et6een them7 We ta4e the d or3itals in their real
.orms and 6e note immediately that those .or 6hich the lo3es lie *et0een the Cartesian
aes, i7e7 d
K
, d
yK
and d
y
ha/e Kero o/erlap, and hence Kero interaction 6ith the hydrogen
atoms7 This is 3ecause each hydrogen #s or3ital has an e0ual and opposite o/erlap 6ith
the lo3es o. the a3o/e d2or3itals 6hich lie on either side o. it (Digure -7%+7 By contrast, the
d

y
2 and d
K
2 or3itals, 6hich are directed along the Cartesian aes, o/erlap strongly 6ith
their neigh3ouring hydrogen #s or3itals7 We can already see here the 3asis o. a distinction
+N 95
R
F
9*
9,
9# 92
+F
+R
N
9?
6ig;re +1+ "ctahedral C9
?
molecule
]
The phrase Qat the n1cle1s G may appear a little strange, 3ut 6e are tal4ing here not o. the dipole2dipole 3ut the Dermi2contact
interaction .or 6hich the electron has to ha/e a Lnite pro3a3ility o. actually 3eing at the nucleus o. the atom in 0uestion7
Carrington and CcLachlan
%
gi/e a nice treatment o. the theory in/ol/ed7 See also Section *7$7
9

d

2
y
2 d
K
2 $
#
$
2
$
,
$
*
$
5
$
?
d

2
y
2 Ed 0


,K


,K
0 0
d
K
2 0 Ed K K K K 2K 2K

,K

,K
N
R

+
+
+ F
+

+
F
+
+
+
+

I
+

"/erlap o. d
K
6ith
9#, 9,, 95 and 9?
6ig;re +1, Atomic or3ital o/erlap in C9
?
"/erlap o. d

2
y
2
6ith
9#, 92, 9, and 9*
3et6een these t6o sets o. d or3itals 6hich is central to the success o. the CD theory7 The
o/erlaps 6hich 6e re0uire may 3e epressed in terms o. an ar3itrary parameter, ' , as
.ollo6s1
d
K
2 |$
#
= d
K
2 |$
2
= d
K
2 |$
,
= d
K
2 |$
*
= '
d
K
2 |$
5
= d
K
2 |$
?
= 2'

d

2
y
2
|
$
#
=
d

2
y
2
|
$
2
=
d

2
y
2
|
$
,
=
d

2
y
2
|
$
*
=

,'
And 6e assume that the interactions, 6hich 6e epress in the .orm o. a 9amiltonian
energy matri (Appendi ,+, are proportional to these o/erlaps1
,K ,K
$
#
Es 0 0 0 0 0
$
2

,K

K 0 Es 0 0 0 0
$
,

,K K 0 0 Es 0 0 0
$
*

,K

K 0 0 0 Es 0 0
$
5
0 2K 0 0 0 0 Es 0
$
?
0 2K 0 0 0 0 0 Es
An this matri, Ed and Es are the energies o. the metal d or3itals and hydrogen #s
or3itals respecti/ely7 The o..2diagonal elements are the interaction energies epressed in
terms o. a parameter K , proportional to ' , 6hich, .or our present purposes, 6e do not
need to 0uanti.y .urther7 When the matri is diagonalised (Bo -7*+ 6e Lnd .our
eigen/alues o. Es7 The eigen.unctions that correspond to these eigen/alues are
com3inations o. hydrogen
#s or3itals 6hich do not ha/e the correct symmetry, e
g
or t
2g
, to com3ine 6ith any o. the
metal d or3itals7 We also Lnd t6o eigen/alues o.1
Ed
+
Es


!Ed

Es"
2
+
*%K
2
and t6o o.1
E
3
=
E
a
=
2
Ed + Es +

!Ed Es"
2
+ *%K
2
2
These energies are those o. the 3onding, E
3
, and anti3onding, E
a
, molecular or3itals
.ormed 3y interaction o. the metal d

y
2 and d
K
2 or3itals 6ith com3inations o. the hydro2
gen #s or3itals o. the hydrogen atom ligands 6hich ha/e the same symmetry7 Since the
d or3itals are 3oth o. e
g
symmetry the molecular or3itals must also 3e o. e
g
symmetry7
The symmetry is conLrmed 3y the .act that 6e ha/e a degenerate pair o. 3onding and a
degenerate pair o. anti23onding or3itals7 As 6e ha/e seen a3o/e, the hydrogen atoms o.
our C9
?
molecule o..er no or3itals suita3le .or com3ination 6ith metal d or3itals o. t
2g
symmetry, so the d
K
, d
yK
and d
y
or3itals o. the metal ta4e no part in the 3onding and
remain triply degenerate 6ith energy Ed, 6hich lies 3et6een the 3onding and anti3onding
e
g
molecular or3itals7 9o6e/er, 6here the ligands ha/e /alence p or3itals interaction 6ith
the d
K
, d
yK
and d
y
or3itals o. the metal is possi3le and triply degenerate 3onding and
anti3onding molecular or3itals result7 Thus the C" model reproduces all the essential
.eature o. the CD7 "ur results .or the C9
?
comple are illustrated in Digure -7$7
Thus .ar, the energy2le/el scheme a3o/e reOects the CD scheme 0uite 6ell 3ut a
pro3lem arises 6hen 6e as4 6hich energy le/els are occupied and 6hich unoccupied7
Si hydrogen atoms pro/ide si electrons, .our o. 6hich 6ould Lll the lo6est pair o. e
g
le/els lea/ing t6o .or the three t
#u
and the a
#g
le/els7 There.ore, at least se/en d electrons
.rom the metal are re0uired 3e.ore any enter the t
2g
and e
g
le/els, the occupation o. 6hich
is central to the CD model7 "ur simple C" model o. C9
?
appears to 3e at odds 6ith
the CD description7 But 6e should recall that in the ma@ority o. simple transition2metal
complees the ligands each donate t6o electrons to the structure7 These t6o electrons are
usually a lone pair, as 6e see /ery clearly in the coordination complees o. 6ater and
ammonia7 A. 6e assume that the hydrogen #s or3itals 6e ha/e used are, in e..ect, lone
pair or3itals containing t6o electrons, all the essentials, including the symmetry, o. the
energy2le/el scheme (Digure -7$+ remain unchanged, 3ut 6e no6 ha/e #2 ligand electrons
at our disposalP @ust enough to Lll the si lo6est le/els, i7e7 e
g
, t
#u
and a
#g
7 Any
metal d electrons must then occupy the t
2g
and e
g
le/els, in ecellent correspondence
6ith the CD model7
The pairs o. 3onding and anti3onding 6a/e .unctions .or the energy le/els o. e
g
symmetry 3ear closer scrutiny7 They arise .rom t6o identical 2 2 matrices (see Bo -7*+
and there.ore ha/e the same .orm in 3oth cases7 Ta4ing, as our eample, the com3ination
'nergy
e
g
2 anti3onding molecular or3itals
, uncom3ined metal d or3itals
t
2g
5 metal d or3itals
? hydrogen #s atomic or3itals
t
#u
+ a
#g
* uncom3ined hydrogen #s or3itals
e
g
2 3onding molecular or3itals
? 9
C9
?
C
6ig;re +1- Colecular or3ital energy2le/el scheme .or C9
?
Bi3liography and Durther :eading 20,
o. ligand or3itals,
eg!K
2
"
, 6hich 3onds to the d
K
2 metal or3ital, 6e can 6rite the 3onding
and anti3onding molecular or3itals in the .orms1

3onding
= =d
K
2 + [
eg!K
2
"
and
anti3onding
= [ d
K
2 =
eg!K
2
"
6here =
2
+ [
2
= #.0 i. or3ital o/erlap 3et6een the d or3itals and the hydrogen #s or3itals
is neglected in the normalisation7 At one etreme 6here [ = #.0 and = = 0.0 6e ha/e
the CD theory7 The lo6er2energy C",
3onding
, is composed solely o. ligand or3itals,

eg!K
2
"
, and the higher2energy C",
anti3onding
, is a pure d
K
2 or3ital o. the metal7 The
three uncom3ined metal d or3itals o. t
2g
symmetry lie immediately 3elo6 the latter7
When [ = #,

2 ([ and = 6ill only 3e eactly e0ual to #,

2 6hen Ed = Es+
6e ha/e !aulingGs co/alent /alence 3ond description
2
6ith metal d2or3itals and ligand
or3itals contri3uting approimately e0ually to the t6o molecular or3itals7 An principle, a
high20uality C" calculation 6ill determine @ust 6here 6ithin this range o. possi3ilities a
particular comple lies7 But e/en today C" or <DT calculations 6ith such a large num3er
o. electrons present considera3le pro3lems7 Comprehensi/e pac4ages 3y means o. 6hich
these theories can 3e applied to transition metal complees are a/aila3le 3ut their modi
o%erandi re0uire care.ul study i. they are to 3e used 6ith conLdence and the limitations
on their results understood7
An an important semi2empirical de/elopment, :oald 9o..man proposed his Qetended
9uM c4el theoryG7 Catri elements analogous to Es, Ed and K a3o/e are represented
3y parameters the /alues o. 6hich are o3tained 3y Ltting the results o. trial calculations to
eperiment7 The inter2or3ital 3onding interactions are determined 6ith re.erence to the
corresponding o/erlaps as 6e ha/e done .or K a3o/e, 3ut in a more sophisticated manner7
'lectron repulsion is not considered eplicitly7 Though purists ha/e sometimes 3een rather
scathing a3out the theory, it has .ound 6idespread application and acceptance in the semi2
0uantitati/e interpretation o. some o. the /ast 0uantity o. data 6hich organo2metallic
chemists in particular ha/e generated in the last 50 years7
+1, 8I85I2RA!HY AN3 6URTHER REA3IN
#7 97L7 SchlaM.er and G7 Gliemann, /asic Princi%les of Ligand 9ield -heory, Wiley2
Anterscience, London, #$?$7
D7A7 Cotton, Chemical A%%lications of .ro1% -heory, 2nd edn, Wiley2Anterscience, ;e6 Ror4,
#$-#7
C7J7 Ballhausen, :ntrod1ction to Ligand 9ield -heory, CcGra629ill, ;e6 Ror4, #$?27
S7B7 !iepho and !7;7 SchatK, .ro1% -heory in S%ectrosco%y, Wiley2Anterscience, ;e6 Ror4,
#$%,7
Z9elp.ul introductions to group theory may 3e .ound in1
S7D7A7 >ettle, Symmetry and Str1ct1re, 2nd edn, Wiley, ;e6 Ror4, #$$57
G7 <a/idson, .ro1% -heory for Chemists, CacCillan, London, #$$#7\
27 L7 !auling, -he Nat1re of the Chemical /ond, 2nd edn, Cornell =ni/ersity !ress, Athaca, #$*07
,7 97 'yring, J7 Walter and G7'7 >im3all, 31ant1m Chemistry, Wiley, ;e6 Ror4, #$**7
*7 J7S7 Gri.Lth, -he -heory of -ransition+5etal :ons, Cam3ridge =ni/ersity !ress, #$?#7
57 W7 Lo6, Oeit. %hysi;. Chem., %', #0- (#$5-+7
?7 J7J7 Aleander and 97B7 Gray, Q. Amer. Chem. Soc., -., *2?0 (#$?%+7
-7 A7B7!7 Le/er, :norganic Electronic S%ectrosco%y, 2nd edn, 'lse/ier, ".ord, #$%*7
%7 A7 Carrington and A7<7 CcLachlan, :ntrod1ction to 5agnetic Resonance, 9arper & :o6,
London, #$?-7
20* Transition2Cetal Complees
*5 *5
2
#

(
#
,5

+2
82D +1% Cal#;lation o" an ang;lar integral
'ample o. the e/aluation o. an angular integralP R
22
|R
**
|R
2+2
A7
Since R| re0uires that 6e ta4e the comple con@ugate o. R 6e ha/e1
and
R
2

2
| = |S
2
+
2
=
2
+
2
!# "
+
2
!$" =

#5
sin
2
*
#
#

2(
ep!2i$"
R
*

*
=
*

*
!# "

*
!$" =
There.ore the integral A is1
, ,5
sin
*
#?
#
#

2(
ep!

*i$"
*5

,5 # #

(
%

2(
A
=
25?

2(

2(
sin
0
# sin # d#
0
ep!0" d$
The integration o/er $ gi/es a multiplicati/e .actor o. 2( 7
At is perhaps 6orth noting here that, had the argument o. the eponential 3een
anything other than Kero, in$ say, then the result o. the integration 6ould 3e Kero
3ecause sin(n$+ is Kero at 0 and 2( 6hile cos!n$" = # at 3oth limits and the t6o /al2
ues cancel7 9ence the re0uirement that the m /alues o. the three spherical harmonics,
allo6ing .or a change o. sign o. the Lrst, sum to Kero7
;o6, setting

sin
2
#
=
cos
2
#

# and using the su3stitution
=
cos # d
=
sin # d# , 6e ha/e1

,5
%

#
2 *
A
=
25?

2(
sin
0
# sin # d# =
25?

2( #
!x #" d
'pansion o. the 3rac4et and integration o. the resulting polynomial in gi/es1
*5

,5 #

# * ? * *5

,5 # 25?

5
A
=
25?

2(

2
$

-
+
5

,
+
#
=
25?

2(

,#5
=
#*(
82D +1& Cal#;lation o" t$e matrix elements o" 9
)
#"
"or t$e
'
6 state o" /
&
in an
o#ta$e/ral Bel/
The calculation o. the matri elements o. 9

c.
6ill 3e illustrated 6ith the eample
o. the element, , ,|9

c.
|, , 7
'panding each Slater determinant, and noting that 6e must e/aluate 9

c.
.or each
electron and sum their contri3utions, 6e ha/e1
, ,|9

c.
|, ,
= !
#
" { G !#" G
+
#
!2" G
+#
!#" G
+
2
!2"|9

c.
!#"|G
+2
!#" G
+
#
!2"
G
+#
!#" G
+2
!2" }
2
+2
+ !
#
" { G
!#" G
+
#
!2" G
+# !#" G
+
2
!2"|9

c.
!2"|G
+2 !#" G
+
#
!2"
G
+#
!#" G
+2
!2" }
6here the l su3script, 6hich is al6ays 2 .or d or3itals, has 3een omitted to simpli.y
the notation7
But, in 0uantum mechanics all electrons are indistinguisha3le, so each o. the a3o/e
t6o terms must gi/e the same result and 6e may there.ore 6rite1
, ,|9

c.
|, ,
= G
+2
!#" G
+#
!2" G
+#
!#" G
+2
!2"|9

c.
!#"|
G
+2
!#" G
+#
!2" G
+#
!#" G
+2
!2"
'ach o. the .our com3inations o. 3ra 6ith 4et gi/es rise to a product o. t6o
integrals, one o/er each electron1
G
+2
!#" G
+#
!2"|9

c.
!#"|G
+2
!#" G
+#
!2"
= G
+2
!#"|9

c.
!#"|G
+2
!#" G
+#
!2"|G
+#
!2"
The Lrst o. these integrals epresses the interaction o. an electron in a d
+
2
A" 6ith
the crystal Leld and its /alue has 3een sho6n in Section -72 to 3e ,? (neglecting
as 3e.ore+7 The second is #70 3ecause the d or3itals are normalised7 Thus, neglecting
the rise in the d2or3ital centre o. gra/ity, 6e ha/e1
G
+2
!#" G
+#
!2"|9

c.
!#"|G
+2
!#" G
+#
!2" = + ,?
Similarly1
3ut1
G
+
#
!#" G
+
2
!2"|9

c.
!#"|G
+
#
!#" G
+
2
!2" = G
+
#
!#"|9

c.
!#"|G
+
#
!#"
G
+2
!2"|G
+2
!2" = 2 ,,
G
+
2
!#" G
+
#
!2"|9

c.
!#"|G
+
#
!#" G
+
2
!2" and
G
+#
!#" G
+2
!2"|9

c.
!#"|G
+2
!#" G
+#
!2"
are 3oth Kero 3ecause G
+#
!2"|G
+2
!2" = G
+2
!2"|G
+#
!2" = 07
As it happens,

G
+2
!#"
|
9

c.
!#"
|
G
+#
!#"

is also Kero7
An total there.ore1
, ,|9

c.
|, , = { ,? 2 ,,} = ,2.
82D +1' Cal#;lation o" t$e inter9ele#troni# rep;lsion "or some states o" /
&
The general t6o2electron repulsion integral ta4es the .orm1



2 2
a
!#"
3
!2" e ,r
#2

c
!#"
d
!2" d[
#
d[
2

a!#"*!2"
|
e ,r
#2
|
c!#"d!2"

r
# 2
r
,
r
5
# 2
# 2
There are t6o special .orms o. the integral7
The Coulom3 integral, Q (a,3+, in 6hich a = c and 3 = d, represents the mutual
repulsion o. an electron ha/ing the distri3ution
a


a
and an electron 6ith the dis2
tri3ution
3


3
7
The echange integral, @ (a,3+, in 6hich a = d and 3 = c, represents the mutual
repulsion o. the t6o o/erlap distri3utions
a


3
7
But integrals 6hich 3elong to neither o. these special cases are .re0uently encoun2
tered and all non2Kero t6o2electron repulsion integrals 3et6een d2or3ital distri3utions
are listed in the t6o ta3les 3elo67
The angular parts o. the integrals are the same 6hate/er the principal 0uantum
num3er, n7 But the radial .unctions, :
i
, and hence the radial parts o. the integrals
/ary 6ith n and .rom metal ion to metal ion, depending upon its en/ironment etc7
This dependence upon radial .unction is contained 6ithin the radial integrals, D
0
, D
2
and D
*
6hich, .or d2or3ital .unctions, are deLned as .ollo6s1

D
0
=
#
#
:
a
!#":
3
!2"
R

:
c
!#":
d
!2"r
2
r
2
dr
#
dr
2
r
2
D
2
=
*$
#
D
*
=
**#
:
a
!#":
3
!2"
P
R
r
*
:
a
!#":
3
!2"
P
R
:
c
!#":
d
!2"r
2
r
2
dr
#
dr
2
:
c
!#":
d
!2"r
2
r
2
dr
#
dr
2
in 6hich r
R
is the greater and r
P
the lesser o. r
#
and r
2
7
The D
0
, D
2
and D
*
gi/en in Ta3les B-7,7# and B-7,72 include the .actors o. #H*$
and #H**# in D
2
and D
*
respecti/ely7
An ligand Leld theory, the D
4
are usually treated as ad@usta3le parameters and they
are .re0uently ta4en in the con/enient com3inations Lrst suggested 3y :acah 6ho
deLned1
A = D
0
*$D
*
B = D
2
5D
*
and C = ,5D
*
Ele#tron rep;lsion in t$e T
%
an/ T
&
states o" t$e #onBg;ration Ft
&g
G
%
Fe
g
G
%
A (t
2g
+
#
(e
g
+
#
conLguration o. T
2
symmetry is (y+
#
(K
2
+
#
6hich 6hen 6ritten as
an epanded Slater determinant is1
!#,

2"{y!#" K
2
!2" K
2
!#"y!2"}
The mutual repulsion o. the t6o electrons is1
# 2 2 2 2 2
2

y!#"K !2"

K !#" y!2"
|
e ,r
#2
|
y!#" K !2"

K !#" y!2"

# 2 2 2 2 2 2
=
2
{
y!#" K !2"
|
e ,r
#2
|
y!#" K !2"
+
K !#" y!2"
|
e ,r
#2
|
K !#" y!2"

y!#" K
2
!2"| e
2
,r
#2
|K
2
!#" y!2" K
2
!#"y!2"| e
2
,r
#2
|y!#" K
2
!2" }
# 2 2 2 2 2 2
=
2
{
Q !y, K "
+
Q !y, K "

@!y, K "

@!y, K "
} =
Q !y, K "

@!y, K "
2
5

5
#0 #0
Which, using Ta3le B-7,7#1
= D
0
*D
2
+ ?D
*
!*D
2
+ #5D
*
" = D
0
%D
2
$D
*
"r in terms o. :acah parameters1
= A %B = A % ,#5
6here is the energy di..erence 3et6een the
,
! and
,
D states o. d
2
as deLned in
Section -7,72 and calculated 3elo67
Similarly, a (t
2g
+
#
(e
g
+
#
conLguration o. T
#
symmetry is (y+
#
!
2

y
2
"
#
6hich
6hen 6ritten as an epanded Slater determinant is1
!#,

2"{y!#"
2
y
2
!2"
2
y
2
!#"y!2"}
Dor 6hich the mutual repulsion is1
Q !y,
2
y
2
" @!y,
2
y
2
" = D
0
+ *D
2
,*D
*
!,5D
*
" = D
0
+ *D
2
?$D
*
"r in terms o. :acah parameters1 = A + *B = A + * ,#5
3etermination o"
To calculate 6e epress the
,
! and
,
D states o. d
2
as in Section -7,7# and
Appen2 di #01
,
D = | + 2
+
!#" +#
+
!2" = !

#
"{!2 #" !# 2"}
,
! =

!
2
"| + 2
+
!#" #
+
!2"

!
,
"| + #
+
!#" 0
+
!2"
=

!
2
"{!2 #" !# 2"}

!
,
"{!# 0" !0 #"}
Since all components o. a term ha/e the same energy, e/en 6hen inter2electronic
repulsion is included, 6e can ta4e any component to calculate the electron repulsion7
An each case 6e ta4e the component o. the term 6hich has the maimum 5
S
and 5
L
/alues since these ha/e the simplest 6a/e .unctions7 'ach o. the three microstates is
a 2 2 Slater determinant 6hich has 3een epanded a3o/e 6ith a simpliLcation o.
the notation 6hich assumes that the electrons in the state sym3ols are al6ays in the
order #, 27 ;o6, .or
,
D 6e ha/e1
# 2
2

!2 #"

!# 2"
|
e ,r
#2
|
!2 #"

!# 2"

# 2 2
=
2

!2 #"
|
e ,r
#2
|
!2 #"
+
!# 2"
|
e ,r
#2
|
!# 2"

!2 #"| e
2
,r
#2
|!# 2" !# 2"| e
2
,r
#2
|!2 #"
Anspection o. the a3o/e .our integrals sho6s that the Lrst t6o are 3oth Coulom3
integrals representing the repulsion o. an electron in a d
+
2
or3ital 6ith one in a
d
+
#
7 The second pair are echange integrals representing the mutual repulsion o. t6o
electron2density distri3utions 6hich are descri3ed 3y the product o. d
+
2
and d
+
#
7
There.ore1
# 2
2

!2 #"

!# 2"
|
e ,r
#2
|
!2 #"

!# 2"

= !2 #"| e
2
,r
#2
|!2 #" !2 #"| e
2
,r
#2
|!# 2" = Q !# 2" @!# 2"
We can no6 loo4 up the electron repulsion integrals in Ta3le B-7,72, 6hich is
the same as Ta3le B-7,7# 3ut 3ased upon the comple rather that the real d or3itals7
We Lnd1
and1

!2 #"
|
e
2
,r
#2
|
!2 #"
=
D
0

2D
2

*D
*
!2 #"| e
2
,r
#2
|!# 2" = +?D
2
+ 5D
*
so that the electron repulsion in the
,
D state is1 D
0
%D
2
$D
*
7
Dor the
,
! state 6e Lnd three contri3utions to the energy1
!
# 2 2
5
"
{
2

!2

#"
|
e ,r
#2
|
!2

#"

2

!2

#"
|
e ,r
#2
|
!

# 2"
}
2 2
=
5
Q !2

#"

5
@!2

#"
=
!
2
"
{
D
0
2D
2
*D
*
,5D
* } =
!
2
"
{
D
0
2D
2
,$D
* } 5
!
, 2
5
2 , ,
#0
"
{
2

!# 0"
|
e ,r
#2
|
!# 0"

2

!# 0"
|
e ,r
#2
|
!0 #"
} =
5
Q !# 0"

5
@!# 0"
=
!
,
"
{
D
0 +
2D
2
2*D
*
D
2
,0D
* } =
!
,
"
{
D
0 +
D
2
5*D
* } 5 5
and a cross2term composed o. integrals 6hich are o. neither Q nor @ type1

2

?

2 2

#0
{
2

!2

#"
|
e ,r
#2
|
!# 0"

2

!2

#"
|
e ,r
#2
|
!0 #"
}

2

?

#2
=
5
{
?D
2
+
5 ?D
*

2 ?D
2
+
#0 ?D
*
} =
!
5
"
{
,D
2
+
#5D
*
}
The total electron repulsion in the
,
! state is there.ore, D
0
+ -D
2
%*D
*
, so that1
= '!
,
!" '!
,
D" = D
0
+ -D
2
%*D
*
!D
0
%D
2
$D
*
" = #5D
2
-5D
*
;ote that in using Ta3les B-7,7# and B-7,72 the integral a(#+ 3(2+|e
2
,r
#2
|c(#+ d(2+ 1
(a+ Will al6ays 3e Kero i. the spin .unction o. or3itals a and c (electron #+ and o. 3
and d (electron 2+ are not the same7 But the spins o. the t6o electrons need not
3e the same7
(3+ 'presses the mutual repulsion o. t6o electron densities a(#+|c(#+ and
3(2+|d(2+ , and electrons are identical7
There.ore1
a!#" 3!2"| e
2
,r
#2
|c!#" d!2" = c!#" 3!2"| e
2
,r
#2
|a!#" d!2"
= a!#" d!2"| e
2
,r
#2
|c!#" 3!2" = c!2" d!#"| e
2
,r
#2
|a!2" 3!#" etc7
5ITERATURE
The monographs 3y Ballhausen
#
and Gri.Lth
*
, noted in the 3i3liography o. Chapter -,
are important sources .or readers 6ho 6ish to ta4e this su3@ect .urther7
K
2
y K yK 0 +

, 5

, "ther
K
2
y yK K 0 +

, 5

, "ther
K
2
K y yK 0
+2

, #0

, "ther

2
Iy
2
y K yK 0 +, #5 "ther

2
Iy
2
y yK K 0
, +#5
"ther
Ta?le 8+1'1% T6o2electron repulsion integrals 3et6een d or3itals in their real .orms
a 3 c d D
0
D
2
D
*
Antegral type
K
2
K
2
K
2
K
2
# +* +,? J
K K K K # +* +,? J
yK yK yK yK # +* +,? J
y y y y # +* +,? J

2
Iy
2

2
Iy
2

2
Iy
2

2
Iy
2
# +* +,? J

2
Iy
2
K
2
Iy
2
K # 2 * J

2
Iy
2
yK
2
Iy
2
yK # 2 * J
y K y K # 2 * J
y yK y yK # 2 * J
K yK K yK # 2 * J
K
2
K K
2
K # +2 2* J
K
2
yK K
2
yK # +2 2* J
K
2
y K
2
y # * +? J
K
2

2
Iy
2
K
2

2
Iy
2
# * +? J

2
Iy
2
y
2
Iy
2
y # +* ,* J
y yK yK y 0 +, +20 >
y K K y 0 +, +20 >
K yK yK K 0 +, +20 >

2
Iy
2
K K
2
Iy
2
0 +, +20 >

2
Iy
2
yK yK
2
Iy
2
0 +, +20 >
K
2

2
Iy
2

2
Iy
2
K
2
0
+
*
K
2
y y K
2
0 +*
K
2
K K K
2
0 +#
K
2
yK yK K
2
0 +#
+#5
>
+#5
>
+,0
>
+,0
>

2
Iy
2
y y
2
Iy
2
0 0
+,5
>
K K
2
K
2
Iy
2
0 2

, +#0

, "ther
yK K
2
yK
2
Iy
2
0 +2

, #0

, "ther
K K K
2

2
Iy
2
0 +

, 5

, "ther
yK yK K
2

2
Iy
2
0

, +5

, "ther
Ta?le 8+1'1& T6o2electron repulsion integrals 3et6een d or3itals in their comple
.orms
m
a
m
3
m
c
m
d
D
0
D
2
D
*
Antegral type
+2 +2 +2 +2 # +* +# Q
+2 +# +2 +# # 2 * Q
+2 +# +# +2 0 +? +5 @
+2 0 +2 0 # * +? Q
+2 0 +# +# 0 +

? 5

? "ther
+2 0 0 +2 0 +* +#5 @
+2 # +2 # # 2 * Q
+2 # +# 0 0

? +5

? "ther
+2 # 0 +# 0 +2

? #0

? "ther
+2 # # +2 0 0 +,5 @
+2 2 +2 2 # +* +# Q
+2 2 +# # 0 ? 5 "ther
+2 2 0 0 0 +* +#5 "ther
+2 2 # +# 0 0 ,5 "ther
+2 2 2 +2 0 0 +-0 @
+# +2 +# +2 # 2 * Q
+# +# +# +# # +# +#? Q
+# +# 0 +2 0 +

? 5

? "ther
+# 0 +# 0 # +2 2* Q
+# 0 0 +# 0 +# +,0 @
+# 0 # +2 0 +2

? #0

? "ther
+# # +# # # +# +#? Q
+# # 0 0 0 # ,0 "ther
+# # # +# 0 +? +*0 @
+# # 2 +2 0 0 ,5 "ther
0 +2 0 +2 # * +? Q
0 +# 0 +# # +2 2* Q
0 +# # +2 0

? +5

? "ther
0 0 0 0 # +* +,? Q
0 0 # +# 0 # ,0 "ther
0 0 2 +2 0 +* +#5 "ther
# +2 # +2 # 2 * Q
# +# # +# # +# +#? Q
# +# 2 +2 0 ? 5 "ther
2 +2 2 +2 # +* +# Q
Antegrals not listed eplicitly may 3e o3tained 3y replacing m
i
3y m
i
across a ro6 or 3y
interchanging m
a
6ith m
d
and m
3
6ith m
c
7 Also see notes in last paragraph o. tet in 3o7
d

2
y
2
eg!
2
y
2
"
2

Ed

0 0 0 0 0 0

eg!K
2
"
0 0 2

,K Es 0 0 0 0

a#g
0 0 0 0 Es 0 0 0

t#u
0 0 0 0 0 Es 0 0

t#uy
0 0 0 0 0 0 Es 0

t#uK
0 0 0 0 0 0 0 Es
y

82D +1( 3iagonalising t$e MH


*
matrix
The easiest 6ay to o3tain the eigen/alues o. the 9amiltonian matri .or C9
?
is 3y
means o. a little group theory7
The molecule 3elongs to the symmetry point group "
h
and it is not di.Lcult to
sho6 that the symmetry o. the molecule is reOected in the .ollo6ing com3inations o.
the hydrogen #s atomic or3itals7 The hydrogen atoms are num3ered as in Digure -7-
and the or3ital com3inations ha/e 3een normalised 6ith neglect o. ligand or3ital
o/erlap, i7e7

$
i
|
$
@
=
)
i@
7


a#g
=
!#,
#
?"
{
$
#
+
$
2
+
$
,
+
$
*
+
$
5
+
$
?
}

eg!
2
y
2
"
=
!
2
"
{
$
#

$
2
+
$
,

$
*
}


eg!K
2
"
=
!#,

#2"
{
$
#

$
2

$
,

$
*
+
2$
5
+
2$
?
}


t#u
=
!#, 2"
{
$
#

$
,
}

t#uy
=
!#, 2"
{
$
2

$
*
}

t#uK
=
!#, 2"
{
$
5

$
?
}
The com3inations o. hydrogen #s or3itals ha/e 3een designated 3y the symmetry
species to 6hich they 3elong, a
#g
, e
g
, t
#u
, and the metal d (
2
Iy
2
, K
2
+ or p (, y,
K+ or3itals 6hich ha/e the same symmetry and 6ith 6hich they 6ill there.ore interact7
Since 6e are not considering metal p or3itals here, the t
#u
com3inations o. hydrogen
#s atomic or3itals 6ill play no part in the 3onding o. C9
?
7 A. 6e no6 re.orm our
9amiltonian matri, replacing the ro6s and columns 6hich 6ere .ormerly headed
3y the indi/idual hydrogen #s or3itals 3y ro6s and columns representing the a3o/e
com3inations o. the hydrogen #s or3itals, 6e Lnd the .ollo6ing matri7 To do this
6e Lrst re2calculate the columns7 The column headed
a#g
, .or eample, is simply
the sum o. the si columns headed $
#
to $
?
di/ided 3y

?7 9a/ing completed the


operation .or the columns, 6e repeat it .or the ro6s and o3tain1
9

2
y
2

d
K
2 ,K
eg!K
2
" a#g t#u t#uy t#uK

eg!
2
y
2
"
2 ,K Es 0 0 0 0 0 0
d
K
2
0 0 Ed 2

,K 0 0 0 0
The use o. symmetrised sets o. ligand or3itals as 3asis .unctions results in a matri
6hich is 3loc4ed outP compare the matri 3ased on the unsymmetrised ligand or3itals
in Section -7-7 The ne6 matri is actually si separate matrices .our o. 6hich are
simply # # matrices 6ith eigen/alues o. Es7 The other t6o are identical 2 2
matrices1
9

d
K
2

eg!K
2
"
9

d

2
y
2 2 2 eg! y "
d
K
2
Ed 2

,K d

2 2 Ed 2

,K

eg!K
2
"
2

,K Es
eg!
2
y
2
"
2

,K Es
=
<
and their eigen/alues, <, can 3e .ound 3y sol/ing the characteristic e0uation (Ap2
pendi ,+1
the roots o. 6hich are1
!Ed

<"!Es

<"

#2K
2
=
0
Ed + Es

!Ed Es"
2
+ *%K
2
2
'ach identical matri gi/es t6o /alues o. < one o. 6hich corresponds to ligand2
metal 3onding (the negati/e sign 3e.ore the s0uare root+ and one to anti3onding7
An Section -7- these pairs o. degenerate le/els are designated E
3
and E
a
respecti/ely7
!R285EMS 62R CHA!TER +
#7 Sho6 that A
**
= A
**
.or $
0
= 0 ( H2 and ( 7 (A
4L
is deLned 3y '0uation
(-7275++7
27 Dollo6 the method in Section -7,7# and Bo -72 to calculate the o..2diagonal matri
element , +2|9

c.
|, 2 .or the
,
D state o. d
2
in an octahedral crystal Leld7
,7 Dollo6 the method in Section -7,72 and Bo -7, to calculate the inter2electronic repul2
sion in the |# 0 component o. the
,
! state o. d
2
in an octahedral crystal Leld7
|# 0 = !2,

5"|2
+
2
+
!#,

5"|#
+
#
+

*7 Consider t6o d
2
conLgurations o. an octahedral transition metal comple, a+ in 6hich
the electrons occupy the d
y
and d
K
or3itals 6ith paired spins and 3+ in 6hich the
electrons occupy the d
y
or3ital only7
=se the in.ormation in Bo -72 to calculate the electron2repulsion energy o. these
t6o conLgurations7 Rou should Lnd1
'lectron repulsion .or conLguration a = D
0
+ D
2
+ #?D
*
7
'lectron repulsion .or conLguration 3 = D
0
+ *D
2
+ ,?D
*
7
Note: The 6a/e .unction .or conLguration a is 3est o3tained 3y recognising that it
must 3e the product o. a spin .unction and a space .unction o. the .orm descri3ed in
Section ##757
57 =se the operator V l

s
=
#
V !l
s

+
l s

"
+
V l s

to dra6 up the #0 #0 matri .or


2
+ + K K
the spin or3it coupling in the conLguration d
#
7 Sho6 that the matri has si eigen/alues
o. +V and * o. ,V ,2, as one 6ould epect .or the states
2
<
5,2
and
2
<
,,2
7
?7 Amagine a tetrahedral, transition2metal comple ion, ZC9
*
\
*

, in 6hich the .our 9

ions are arranged around the central metal atom as sho6n in the Lgure1
d
y
!ro3lems .or Chapter - 2#,
N
*
#
2
,
F
With the aid o. this Lgure you should 3e a3le to con/ince yoursel. that the o/erlaps
o. each o. the .our 9

#s A"s 6ith the d
y
, d
K
and d
yK
A"s o. the metal are e0ual in
magnitude 3ut depend .or their sign upon the sign o. the nearest lo3e o. the d2or3ital7
'0ually, it should 3e clear that the o/erlap o. the d

2 2
A" 6ith each o. the 9

#s
A"s is Kero7 Rou can see that this is also the case .or the d
K
2
A" 6hen you recall that
d
K
2
= !#,

,"!d
K
2
2 2

+
K y
2
"7
Assuming that there is Kero o/erlap o. the 9

#s A"s 6ith each other, dra6 up an
energy matri .or the C9
*
comple li4e the one .or C9
?
in Section -7-7 <iagonalise
the matri 3y re.orming the columns and ro6s using the .ollo6ing com3inations o.
the 9

#s A"s1

y
=
#
!s
#

s
2

s
,
+
s
*
"
K
=
#
!s
#
+
s
2

s
,

s
*
"
2 2

yK
=
#
!s
#

s
2
+
s
,

s
*
"
s
=
#
!s
#
+
s
2
+
s
,
+
s
*
"
2 2
Rou should Lnd t6o sets o. triply degenerate le/els, one pair o. dou3ly degenerate
le/els and one singly degenerate le/el7
Assuming that1
a+ the initial energy o. the L/e d2or3itals is 50 #0
,
cm

#
3+ the initial energy o. the #s or3itals o. the .our 9

ions is

##0

#0
,
cm

#
c+ 6here the o/erlap is positi/e (negati/e+, the interaction energy o. an interacting
d2or3ital 6ith an 9

#s or3ital is !+"#5 #0
,
cm

#
7
sho6 that 6e epect the d2d transition o. a d
#
comple 6ith this structure to 3e .ound
in the region o. #2.5 #0
,
cm

#
7
Chapter %
Spe#tros#op0
%70 The interaction o. radiation 6ith matter . . . . . . . . . . . . . . . . . . . . . . . . 2#?
%7# 'lectromagnetic radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#?
%7#7# The electric Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#-
%7#72 The magnetic Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#$
%72 !olarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#$
%727# Linearly polarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
%7272 Circularly polarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22#
%7, The electromagnetic spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
%7,7# Three .orms o. electromagnetic radiation . . . . . . . . . . . . . . . . . 222
%7* !hotons and their properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22,
%7*7# 8elocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22,
%7*72 'nergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*7, Cass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*7* Linear momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*75 Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%7*7? !arity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%75 Selection rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%757# The Bohr I 'instein condition . . . . . . . . . . . . . . . . . . . . . . . . . 22?
%7? The 0uantum mechanics o. transition pro3a3ility . . . . . . . . . . . . . . . . . . 22-
%7- The nature o. the time2independent interaction

$
.
|
V

! y K"
|
$
i

. . . . . . . . 2,,
%7-7# The transition dipole moment . . . . . . . . . . . . . . . . . . . . . . . . . 2,*
%7-72 The relati/e intensities o. =8 I 8AS, A: and ;C:
transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2,%
%7-7, The particle and 6a/e /ie6s o. spectroscopic transitions . . . . . . . 2*2
%7% Spectroscopic time scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*5
%7$ &uantum electrodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*-
%7#0 Spectroscopic units and notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*-
%7#07# The energyH.re0uencyH6a/elength ais . . . . . . . . . . . . . . . . . . . 2*%
%7#072 The intensityHa3sor3ance ais . . . . . . . . . . . . . . . . . . . . . . . . . 2*$
%7## The 'instein coe.Lcients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
%7#2 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
!ro3lems .or Chapter % . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25$
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
2#? Spectroscopy
,1. THE INTERACTI2N 26 RA3IATI2N 4ITH MATTER
Spectroscopy may 3e deLned as the study o. the interaction o. electromagnetic radia2
tion 6ith matter7 Ats application to chemistry, essentially in the second hal. o. the 20th
century, has 3een primarily responsi3le .or the detailed 4no6ledge o. the structure o.
molecules 6hich 6e no6 ha/e7 Chemistry, as 6e 4no6 it today, is inetrica3ly ent6ined
6ith the methods o. molecular spectroscopy and totally dependent upon them7 At is the
purpose o. this chapter to outline the principles o. atomic and molecular spectroscopy
.rom a 0uantum mechanical point o. /ie67 This 6ill help us to understand, in general
terms, ho6 electromagnetic radiation interacts 6ith matter and ho6 in.ormation a3out the
structure o. molecules can 3e o3tained 3y studying that interaction7 The speciLc 3ranches
o. spectroscopy 6hich are o. particular importance to chemistry I electronic, in.rared and
nuclear magnetic resonance I 6ill 3e discussed in the .ollo6ing chapters7 "ur Lrst tas4 is
to set do6n a suita3le description o. electromagnetic radiation7
,1% E5ECTR2MANETIC RA3IATI2N
There 6ere .e6 de/elopments in the science o. optics during the #%th century and, .or
the most part, ;e6tonGs corpuscular /ie6 o. light held s6ay7
#
An the present contet, it
is interesting to note that the generalisation o. ;e6tonian mechanics 3y Lagrange and
Laplace, 6hich 6as also 3elie/ed to 3e applica3le to particles o. light, 6as at least par2
tially responsi3le .or the general conLdence in the corpuscular description o. light at the
end o. that century7 ;e/ertheless, in #%0# Thomas Roung (#--, I #%2$+ re/i/ed the
6a/e theory o. Christian 9uygens (#?2$ I #?$5+ 3ecause he had come to 3elie/e that
colours might 3e associated 6ith /i3rations o. light as notes are associated 6ith
sound /i3ra2 tions7 Later in the century, t6o Drench amateur scientists, Armand DiKeau
(#%#$ I #%$?+ and Jean Doucault (#%#$ I #%?%+, independently impro/ed the accuracy
6ith 6hich the /elocity o. light could 3e measured and Doucault sho6ed that light tra/els
more slo6ly in 6ater than in air7 This result is in agreement 6ith the prediction o. the 6a/e
theory 3ut in contradiction to the corpuscular theory o. light7 An the years #%?* to #%-,,
6hich imme2 diately .ollo6ed DoucaultGs researches, James Cler4 Ca6ell (#%,# I
#%-$+ de/eloped a mathematical theory o. light in the .orm o. .our di..erential e0uations
6hich descri3e light as oscillating electric and magnetic Lelds7 The ne6 theory o.
electromagnetic radiation 6as a triumph7 ;ot only did it sho6 ho6 electricity,
magnetism and light are connected, a .act Lrst demonstrated eperimentally 3y Cichael
Daraday (#-$# I #%?-+ in #%*?, 3ut it made the relationships 0uantitati/e7 An Ca6ellGs
time, electricity 6as measured in one o. t6o units7 At could 3e measured either in terms
o. charge in electrostatic units (e7s7u7+ or in terms o. its magnetic e..ect in electromagnetic
units (e7m7u+7 Ca6ell deri/ed the simple relationship 3et6een these t6o units in 6hich
electricity might 3e measuredP he .ound that1
/alue in e7s7u. = /elocity o. light /alue in e7m7u. !%.#.#"
in agreement 6ith the eperimental disco/ery o. this result 3y >irchho.. in #%5-7
But Ca6ellGs description o. /isi3le light as electromagnetic radiation 6ent much
.urther7 Though 4no6ledge o. the /isi3le spectrum is clearly as old as man himsel.,
only the spectral regions immediately ad@acent to /isi3le light 6ere 4no6n in Ca6ellGs
#0
-
#0
$
, #0
#-
#0
5
#0
-
,

#0
#5
'lectromagnetic radiation 2#-
day7 The near in.rared, 6hich ad@oins the /isi3le on the long26a/elength side, 6as dis2
co/ered 3y Sir William 9erschel (#-,% I #%22+ in #%00 and the ultra/iolet, on the
other side o. the /isi3le, 6as .ound 3y Johann Wilhelm :itter (#--? I #%#0+ in
#%0#7 But Ca6ellGs e0uations predicted that there 6as an inLnite spectrum o.
electromagnetic radiation, @ust 6aiting to 3e disco/ered, outside the then24no6n range7
This prediction 6as 3rilliantly conLrmed .or long 6a/elengths 3y 9einrich :udol.
9ertK (#%5- I #%$*+ and in modern spectroscopy 6e ma4e use o. a spectral range o.
.re0uency (or 6a/e2 length+ 6hich co/ers approimately #2 po6ers o. ten (Ta3le %7#+7
Ca6ellGs e0uations passed through the great uphea/als 6hich o/ertoo4 theoretical
physics at the 3eginning o. the 20th century 0uite unchanged7 They pro/ide us 6ith a
description o. electromagnetic radiation 6hich is /ery /alua3le 6hen 6e 6ish to
consider ho6 that radiation interacts 6ith matter, the process 6hich is the 3asis o.
spectroscopy7 We there.ore no6 eamine this description7
,1%1% T$e ele#tri# Bel/
Amagine (Digure %7#(a++ an electric Leld represented 3y a /ector E
0
6hich is rotating in
the yK2plane 6ith an angular /elocity o. A radians per second7 Dor this /elocity the time,
t

, re0uired 3y the /ector E
0
to eecute one complete re/olution is1
t

= 2(,A !%.#.2"
Ta?le ,1% The regions o. the electromagnetic spectrum
Branch o. spectroscopy ;ominal 3oundary
a
<Hm > Hcm

#
>Hm

#
>Hs

#
F2ray
Auger
#0

##
#0
$
#0
##
,

#0
#$
#0

$
8acuum ultra/iolet #0

-
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 #0

-
=ltra/iolet
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 ,.% #0

-
8isi3le
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 -.% #0

-
;ear in.rared #0

?
#0
*
#0
?
, #0
#*
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 , #0

?
An.rared #0

5
#0
,
#0
5
, #0
#,
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 , #0

5
Dar in.rared #0

*
#0
2
#0
*
, #0
#2
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 , #0

*
Cicro6a/e
2 2 2 2 2 2 2 2 2 2 2 #0

,
#0 #0
,
, #0
##
'lectron paramagnetic resonance
2 2 2 2 2 2 2 2 2 2 2 #0

2
# #0
2
, #0
#0
;uclear magnetic resonance
2 2 2 2 2 2 2 2 2 2 2 #0 #0

,
#0

#
,

#0
-
a
Set .or the range #0

%
to , #0

*
m in :eport ;o7 ? o. the Joint Committee on ;omenclature in Applied
Spectroscopy, Analytical Chemistry, 25, #,*$ (#$52+7
2#% Spectroscopy
E
y
0
E
0
+#70
R
+075
070
075 N
#70
0 = 6t g 0p 0 #p 2p ,p *p 5p
(a+
E
y
= E
0
l
l
+#70
+075
070
075
#70
t = 2Hv
K = (n 2+cHv
t = #Hv
K = (n #+cHv
(3+
t = 0
K = ncHv
6ig;re ,1% Graphs o. E
0
/ersus # (a+ and t (3+
The in/erse o. this time is the .re0uency o. re/olution, >, in s

#
, there.ore1
> = A,2( !%.#.,"
A. the tail o. the /ector is Led, then its head descri3es a circle in the yK2plane and the
angle, # , 3et6een the K2ais and the /ector is gi/en 3y '0uation (%7#7*+1
# = At !%.#.*"
and the component o. E
0
in the y2direction, E
y
, is1
E
y
= E
0
sin!# " = E
0
sin!At " !%.#.5"
Thus, the electric Leld in the y2direction, E
y
, /aries 6ith time as a sine .unction and
oscillates as illustrated in Digure %7#(a+7
An Ca6ellGs description, this oscillating electric Leld propagates through space in a
direction, usually chosen to 3e K, at $0

to the oscillation direction, 6ith the /elocity o.
light, c7 There.ore, a particular Leld /ector, E
y
(0+ generated at time t = 0, mo/es a6ay
.rom the light source at /elocity c7 An the time, t

= #,>, re0uired 3y the rotating /ector E
0
to complete one cycle, the propagating E
y
/ector 6ill ha/e mo/ed along the K2direction
to a position K = ct

= c,> and a.ter n cycles 6hen # = 2n( , E
y
6ill ha/e reached K
= nc,>7 There.ore, eliminating n, # = 2( K>,c7 Thus, the 6a/e reproduces itsel. e/ery
inter/al o. c,> along the K2direction (Digure %7#(3++ and this repeat distance is 4no6n as
the 6a/elength, <, so that1
and
< = c,> or c = <> !%.#.?"
E
y
= E
0
sin!2( K>,c" = E
0
sin!AK,c" !%.#.-"
The dependence o. E
y
upon time ('0uation (%7#75++ and distance ('0uation (%7#7-++
may 3e com3ined to gi/e1
E
y
= E
0
sinZA!t K,c"\ !%.#.%"
6here the t6o parts o. the argument o. the sine .unction are com3ined 6ith the negati/e
sign 3ecause (Digure %7#(3++ i. 6e mo/e along the 6a/e in the positi/e K2direction 6e
are going 3ac46ards in time7 A. this idea presents a pro3lem, consider the light arri/ing
on the earth today .rom a distant star7 The light 6hich 6e no6 see is a record o. e/ents
that too4 place on the star at the time that the light le.t it, many years ago7 But i. 6e
could @ourney to6ards the star, i7e7 in the negati/e K2direction, 6e 6ould see e/er more
recent light until, upon arri/ing at the starGs sur.ace, 6e 6ould see e/ents as they are
currently happening7 The re/erse is true i. 6e mo/e a6ay .rom the star in the direction
o. propagation o. the light7
,1%1& T$e magneti# Bel/
Apart .rom the oscillating electric Leld discussed a3o/e, Ca6ellGs description o. light
also includes a magnetic Leld, $, 6hich oscillates in phase 6ith the electric Leld 3ut
is al6ays directed at $0

to it, i7e7 along in Digure %7#7 Thus, the .ull description is
one o. an electric and magnetic Leld oscillating in phase and orientated at right angles
to each other and to the propagation direction7 These oscillating Lelds, 6hich propagate
through space (/acuum+ 6ith a speed o. 2.$$-$25

#0
%
ms

#
, constitute 6hat 6e call
light in the region 6here 6e can detect it 6ith our eyes and, in general, electromagnetic
(e2m+ radiation7 At is characterised particularly 3y its 6a/elength and .re0uency, 6hich
are related 3y '0uation (%7#7?+7 An much o. the .ollo6ing 6e use the 6ord QlightG rather
than Qelectromagnetic radiationG on account o. its 3re/ity, 3ut the latter is al6ays implied7
,1& !25ARISE3 5IHT
The electric and magnetic Lelds o. a light 3eam oscillate in directions perpendicular to the
direction o. propagation o. the light7 Thus, i. 6e choose K as the direction o. propagation,
E and $ must lie in the y2plane7 (Clearly, 6e could choose any direction .or the direction
o. propagation, 3ut unless it is stated other6ise 6e 6ill al6ays choose K7+ The /ectors
E and $ are .re0uently said to /i3rate, rather than oscillate, in the y2plane7 Light .rom
the usual sources, e7g7 the sun, incandescent metals, electrical discharges has electric and
magnetic /ectors /i3rating in e/ery direction in the y2plane (Digure %72(a++7 But 3y using
optical de/ices 4no6n as polarisers, it is possi3le to o3tain light 6hich /i3rates in only one
direction (Digure %72(3++7 Such light is said to 3e linearly or plane polarised in the direction
in 6hich the E /ector /i3rates7 !olarised light is /ery important in spectroscopy 3ecause
the direction o. polarisation o. the light can ha/e a decisi/e e..ect upon 6hether or not
the light is a3sor3ed 3y a particular sample7 An this connection it is use.ul to distinguish
t6o 4inds o. polarised lightP linearly and circ1larly polarised7 An 6hat .ollo6s 6e shall
mention only the E /ectorP 3ut the $ /ector is al6ays present .ollo6ing eactly the same
pattern o. 3eha/iour as the E /ector, 3ut al6ays at right2angles to it7 Both E and $ are
important, 3ut usually in di..erent .orms o. spectroscopy7
R
E
$
F
=npolarised light
(E /ectors only+
(a+
!lane polarised light
(E and $ /ectors+
(3+
6ig;re ,1& =npolarised light (a+ and linearly (plane+ polarised light (3+
,1&1% 5inearl0 polarise/ lig$t
The electric /ector o. a polarised light 3eam propagating along K may 3e resol/ed onto
any t6o mutually perpendicular directions in the y2plane7 At is o. particular interest in
connection 6ith the relationship 3et6een linearly and circularly polarised light to resol/e
the E /ector onto t6o such aes each o. 6hich lies at *5

to E (Digure %7,+7 We then
Lnd that the t6o components o. the E /ector, E

and E
y
say, .orm t6o 3eams o. linearly
polarised light 6ith mutually perpendicular planes o. polarisation 6hich /i3rate in phase
and ha/e e0ual amplitudeP i7e7 E

=
E
y
=
E ,

27 Thus, a 3eam o. linearly polarised light


can al6ays 3e descri3ed in terms o. t6o 3eams o. linearly polarised light 6ith mutually
perpendicular planes o. polarisation, e0ual E
0
/alues and /i3rating in phase7
E
y
= EH2
E
*5
E

= EH2
6ig;re ,1' :esolution o. plane polarised light into and y components
,1&1& Cir#;larl0 polarise/ lig$t
Light propagating through some crystalline materials, e7g7 gypsum, mica and 0uartK, tra/2
els at di..erent /elocities depending upon the direction in 6hich it is polarised7 By passing
plane polarised light through a plate o. such a material, 4no6n as a 0uarter26a/e plate, it
is possi3le to create a situation 6here3y t6o perpendicular and e0ual E /ectors /i3rate $0

out o. phase so that one is at a maimum 6hen the other is a minimum, and /ice2/ersa,
though only at one speciLc 6a/elength7 The resultant is an E /ector 6hich descri3es
a circle and i. 6e also thin4 o. the propagation o. the light 6a/e along K, then the E
/ector descri3es a spiral, li4e a staircase, and returns to the same orientation e/ery time
the 6a/e ad/ances 3y a 6a/elength (Digure %7*+7 Le.t2 and right2handed spirals can 3e
.ormed 3y suita3le choices o. phase (Digure %75+7 Light ha/ing these properties is 4no6n
as circularly polarised light, LC! and :C! .or the le.t2 and right2handed /ersions respec2
ti/ely7 To ensure that there is no con.usion, 6e must deLne more eactly 6hat 6e mean
3y right2 and le.t2handed spirals7 The con/ention is that i. the head o. the E /ector
mo/es cloc46ise 6hen /ie6ed 3y an o3ser/er loo4ing at the light source then the light is
:C!7 Counter2cloc46ise rotation is LC!7 The physical signiLcance o. these t6o .orms o.
polarised light lies in the angular momentum properties o. the photons 6ith 6hich they
are associated7 This 6ill 3e made clear in Section %7*75 3elo67
!ropagation
and
K direction
0 pH*
0
lH%
pH2
lH*
,pH*
,lH%
p
lH2
5pH*
5lH%
6ig;re ,1( Circularly polarised light I propagation
E
:
= (EH2+(E

cos 2pnt E
y
sin 2pnt+
right2handed
0 = 0 pH* pH2 ,pH*
le.t2handed
E
L
= (EH2+(E

cos 2pnt + E
y
sin 2pnt+
6ig;re ,1) Circularly polarised light I sense o. rotation
+
+

,1' THE E5ECTR2MANETIC S!ECTRUM


There is, in principle, no limit to the 6a/elength and .re0uency o. e2m radiation7 9o6e/er,
as .ar as chemical spectroscopy is concerned, the range o. interest runs .rom < = #0

##
m
(> = , #0
#$
s

#
+ to < = #0 m (> = , #0
-
s

#
+7 This is an etremely large range and
it is di/ided into a num3er o. smaller regions (Ta3le %7#+7 There is, o. course, no sharp
di/ision 3et6een any t6o ranges, 3ut the eperimental techni0ues used .or spectroscopy
in the di..erent regions and the type o. in.ormation o3tained di..er 6idely7 At is there.ore
con/enient to discuss spectroscopy in the di..erent regions o. the e2m spectrum under
di..erent headings, e7g7 ultra/iolet and /isi3le spectroscopy, in.rared spectroscopy etc7, as
6e shall presently see7
,1'1% T$ree "orms o" ele#tromagneti# ra/iation
The e2m radiation generated 3y the rotating electric Leld /ector, E
0
, as descri3ed in
Sections %7# and %72 is called electric di%ole radiation 3ecause it has eactly the same
.orm as the radiation emitted 3y an oscillating dipole composed o. t6o e0ual and opposite
charges, 0
+
and 0

, separated 3y a distance l (Digure %7?(a++ and each /arying 6ith time


according to the e0uation1
0 = 0
=
0
0
cos At
9o6e/er, though this is the most common .orm o. e2m radiation it is not the only one7
T6o other types o. e2m radiation 6ill ma4e occasional appearances in this 3oo47 T6o
identical electric dipoles arranged co2linearly end to end (Digure %7?(3++ 6ith the central
charge and those at the ends /arying in time according to the e0uation1
20

=
0 = 0
0
cos At
emit electric 71adr1%ole radiation7 Dinally, an oscillating electric current Oo6ing in a
loop (Digure %7?(c++ constitutes an oscillating magnetic dipole and emits magnetic di%ole
radiation7
0
+0
+20
0
'lectric
<ipole
0
'lectric h
&uadrupole
(a+ (3+
6ig;re ,1* Three .orms o. electromagnetic radiation
Cagnetic
<ipole
(c+
!hotons and their properties 22,
,1( !H2T2NS AN3 THEIR !R2!ERTIES
Be.ore 6e em3ar4 upon the study o. the interaction o. radiation 6ith matter in particular
regions o. the spectrum 6e must recall (Section 27?+ that, at the end o. the #$th century,
the 6a/e theory o. light 6as .ound to 3e di.Lcult to reconcile 6ith the results o3tained
.rom a study o. the photoelectric e..ectP the e@ection o. electrons .rom a metal sur.ace
6hen that sur.ace is irradiated 6ith /isi3le or ultra/iolet light7 This 6as @ust one o. the
pro3lems pre/alent at that time 6hich, in #$05, led 'instein to propose that processes
6here light is a3sor3ed or emitted 3y a su3stance might 3e 3etter understood in terms o.
light 0uanta or photons o. energy !h>"7 'instein did not himsel. coin the name QphotonGP he
used the term light2energy 0uantum throughout his #$05 paper7 The 6ord photon .or the
corpuscle o. light 6as proposed 3y Gil3ert ;e6ton Le6is (#%-5 I #$*?+ in #$2? and
the suggestion appears to ha/e recei/ed immediate acceptance7 'insteinGs corpuscular
concept o. light 6as success.ully applied 3y Bohr in his #$#, interpretation o. the hydrogen
atom spectrum7 An #$#? it 6as .ully su3stantiated, 6ith respect to the photoelectric e..ect,
3y Cilli4anGs comprehensi/e eperimental studies (Section 27?+, and since that time this
/ie6 o. the energetics o. the interaction o. light 6ith matter has ne/er 3een challenged7 At is
there.ore appropriate that 6e no6 consider some properties o. the photon7
!hotons are the 0uanta o. the electromagnetic Leld7 Li4e other particles, they ha/e
energy, angular momentum and parityP properties 6hich must 3e conser/ed 6hen photons
interact 6ith other 0uantum2mechanical entities such as atoms and molecules7 "ur interest
in these conser/ation re0uirements arises 3ecause they .orm the 3asis o. the spectroscopic
selection rules7 An particular, 6hen a photon is a3sor3ed (emitted+ 3y an atom or molecule
the energy, angular momentum and parity o. the system, photon + atom or molecule, must
3e the same 3e.ore and a.ter the a3sorption (emission+7 This 3ald statement re0uires .urther
elucidation in the case o. the conser/ation o. angular momentum7 An 0uantum mechanics,
6hen t6o angular momenta, @
#
and @
2
, are added together 2@
P
+ # /alues o. the resultant
sum, J, are possi3le, 6here @
P
is the smaller o. @
#
and @
2
(Section *7?7#+7 These /alues
.orm the Cle3sch I Gordan series ('0uation (*7?7#++1
J = @
#
+ @
2
@
#
+ @
2
# @
#
+ @
2
2 . . . |@
#
@
2
|
8alues o. J, @
#
and @
2
6hich satis.y any o. the a3o/e 2@
P
+ # e0uations are said to
satis.y a triangular condition 6hich is 6ritten (@
#
, @
2
, J+ and is not e0ual to Kero only
i.
J is one o. the Cle3sch I Gordan series .ormed .rom @
#
and @
2
7 Thus, i. @
i
, @
.
and @
p
are
the
angular momenta o. the initial state, Lnal state and photon respecti/ely, then these three
angular momenta must satis.y the triangular condition (@
i
, @
p
, @
.
+ i. angular
momentum is to 3e conser/ed in the a3sorptionHemission process7 The .act that 2@
P
+
# di..erent
outcomes can all satis.y the condition .or the conser/ation o. angular momentum seems,
at Lrst sight, a little surprising7 9o6e/er, this is necessary in order to ta4e account o.
3oth a3sorption and emission processes as 6e shall see 6hen 6e consider electric dipole
transitions 3elo67
,1(1% Velo#it0
The /elocity o. the photon is the /elocity o. light, 6hich is e0ual to the product o. the
6a/elength (< in m+ and the .re0uency (> in s

#
+1
c = < > = 2.$$-$25 #0
%
m s

#
!%.*.#"
22* Spectroscopy
The a3o/e Lgure is the /elocity o. light in a /acuum7 An any other medium the /elocity
is less 3y a .actor o. #Hn, 6here n is the re.racti/e inde o. the medium7 Durthermore,
in any medium other than a /acuum the /elocity o. light depends upon its 6a/elength7
The dependence o. /elocity or re.racti/e inde upon 6a/elength is responsi3le .or the
.act that light is dispersed into a spectrum 6hen it passes through a transparent prism7
As a simple illustration o. '0uation (%7*7#+, 6e ta4e one o. a pair o. lines 4no6n as
the sodium < linesP t6o closely spaced atomic spectral lines 6hich are responsi3le .or
the strong yello6 colour o. the sodium Oame or street lamp and 6hich deri/e .rom the
transitions
2
!
,

2
S
#
and
2
!
#

2
S
#
o. the sodium atom (Chapter 5+7 The Lrst o. these
2 2 2 2
lines has <
=
5.%$2

#0

-
m and >
=
5.0%%

#0
#*
s

#
7 At is clear that these data satis.y
'0uation (%7*7#+7
,1(1& Energ0
The energy o. a photon depends upon its .re0uency according to the e0uation proposed
3y 'instein in #$051
E = h> !%.*.2"
h is !lanc4Gs constant, .or 6hich 6e shall use the truncated /alue o. ?.?2? #0

,*
J s
in this section7 Thus, .or the a3o/e <2line photon 6e Lnd1
E = ?.?2? 5.0%% #0

20
= ,.,-# #0

#$
J !%.*.,"
,1(1' Mass
A relationship also deduced 3y 'instein, 3ut in connection 6ith the special theory o.
relati/ity, may 3e used to determine the mass o. a photon1
E = mc
2
or m = E,c
2
!%.*.*"
Dor our particular eample 6e Lnd1
m = ,.,-# #0

#$
,!2.$$% #0
%
"
2
= ,.-5# #0

,?
4g
;ote that, 3ecause the mass o. the photon depends upon its energy, its mass also
depends upon its 6a/elength or .re0uency7 A. 6e also recall that the mass o. a particle
mo/ing 6ith a /elocity, v, compara3le 6ith that o. light is related to its mass 6hen at
rest, m
0
, 3y yet another e0uation due to 'instein1
m
0
= m

# !v,c"
2
!%.*.5"
then 6e see that, 3ecause the photon mo/es 6ith the /elocity o. light, v,c = # and the
rest mass o. the photon is Kero7
,1(1( 5inear moment;m
The linear momentum, %, o. a particle o. mass m mo/ing 6ith /elocity v is gi/en 3y
% = mv and since .or the photon v = c, in a /acuum our <2line photon has a linear
momentum o.1
% = mc = ,.-5# 2.$$% #0

2%
= #.#25 #0

2-
4g m s

#
!%.*.?"
Selection rules 225
ComptonGs interpretation o. the scattering o. F2rays 3y electrons (see Bo %7#+ pro/ides
one o. the most con/incing pieces o. e/idence .or the photon as a discrete particle 6hich
has mass and, hence, linear momentum7
,1(1) Ang;lar moment;m
'periment sho6s that the electric dipole photon has a spin angular momentum charac2
terised 3y a spin 0uantum num3er o. #, i7e7 a total spin angular momentum o.

2h,2(
(Chapter *+7 But, unli4e a particle 6ith a Lnite rest mass, 6hich 6ould ha/e K2components
o. +#, 0 and # in units o. h,2( (Chapter *+, the photon has only t6o components o.
h,2( directed parallel (++ and antiparallel (+ to its direction o. propagation7 These
t6o components o. angular momentum are related to the property o. light 6hich is 4no6n
as polarisation7 As 6e ha/e seen in Section %7272, t6o types o. circularly polarised light
eist7 LC! light has a K component o. angular momentum o. +h,2( and :C! light
has a K component o. angular momentum o. h,2( 7 The photons in a 3eam o. linearly
polarised light are not in states 6hich are eigen.unctions o. the operator .or the K compo2
nent o. angular momentum7 The epectation /alue .or a measurement o. the K component
o. their angular momentum is Kero, since a large num3er o. measurements 6ould record
e0ual num3ers o. photons ha/ing angular momenta o. +h,2( and h,2( 7 An SA units
the angular momentum o. a photon is1
l =

2h,2( =

2 ?.?2? #0

,*
,2( = #.*$# #0

,*
J s !%.*.-"
The /alue o. l has 3een determined eperimentally in a /ery ingenious 6ay 3y Beth7
2
;ote that l is independent o. the 6a/elength or .re0uency o. the photon and is there.ore
the same .or all photons7
,1(1* !arit0
Li4e atomic 6a/e .unctions (Section 57#072+, an odd (u+ or e/en (g+ character may 3e
assigned to photons and, as 6ith atoms, the parity o. the photon depends upon its state7
!arity and angular momentum together lie at the heart o. the stringent conditions 6hich
determine the 6ay in 6hich photons interact 6ith matter7 These conditions are called
selection r1les7
,1) SE5ECTI2N RU5ES
Three com3inations o. photonic angular momentum and parity play a particular role in
the selection rules o. chemical spectroscopy7 'ach corresponds to a particular .orm o.
e2m radiation7
The photons o. electric dipole radiation are o. odd (u+ parity and carry one unit o.
angular momentum7 Dor an allo6ed electric dipole transition, there.ore, the parities o. the
initial and Lnal states must di..er, i7e7 u

g or g

u, and the triangular condition (@
i
,
#, @
.
+ must 3e o3eyed7 Since the total angular momentum 0uantum num3er, @, is al6ays
positi/e, one might nai/ely thin4 that the a3sorption o. a photon must 3e accompanied
3y an increase in the angular momentum o. the a3sor3ing species, and emission 3y a
22? Spectroscopy
decrease7 But the .act that angular momentum is conser/ed i. the resulting @
.
satisLes
any o. the 2@
P
+ # Cle3sch I Gordan relationships remo/es this apparent restriction7 Dor
eample, i. an atom in a ! state (@ = #+ a3sor3s a photon, states ha/ing increased (@ = 2
Z<\+, unchanged (@ = # Z!\+ or decreased (@ = 0 ZS\+ angular momentum may result7 And
in all three cases angular momentum is conser/ed7 9o6e/er, in the case o. the ! !
transition there is no change o. parity, so it 6ould not 3e electric2dipole allo6ed7 'lectric
dipole transitions are responsi3le .or the /ast ma@ority o. the a3sorption (emission+ 3ands
o3ser/ed in the electronic spectra o. atoms and molecules and in all in.rared a3sorption and
emission processes7 They are much stronger (3y a .actor

#0
*
+ than all other transitions
6hich are .or3idden 3y these selection rules7
The photons o. electric 0uadrupole radiation carry t6o units o. angular momentum
and are o. e/en (g+ parity7 The etra angular momentum is usually called or3ital angular
momentum, 3ut the use o. the terms QspinG and Qor3italG in the case o. photons is to a
large etent a matter o. con/enience 3ecause in most cases the t6o cannot 3e separated7
Dor an electric 0uadrupole transition, there.ore, the triangular condition (@
i
, 2, @
.
+
must 3e o3eyed and the parities o. the initial and Lnal states must 3e the same7 The /ery
6ea4
d d (g g+ and . . (u u+ transitions o. gas2phase metal atoms and ions 6ith
open d or . shells are o. this type7
The photons o. magnetic dipole radiation carry one unit o. angular momentum and
are o. e/en (g+ parity7 Dor an allo6ed magnetic dipole transition, there.ore, the triangular
condition (@
i
, #, @
.
+ must 3e o3eyed and the parities o. the initial and Lnal states
must 3e the same7 These transitions are 6ea4 and rarely seen in electronic
spectroscopy and ne/er in the in.raredP 3ut their signiLcance is great 3ecause they are the
transitions 6hich are o3ser/ed in electron and nuclear magnetic resonance
spectroscopies7
The selection rules that deri/e directly .rom the re0uirements o. conser/ation, espe2
cially conser/ation o. energy, angular momentum and parity, impose many restrictions
upon the process o. a3sorption or emission o. a photon 3y a molecule7 The .act that the
selection rules are so restricti/e should not, in general, 3e regarded as a disad/antage7
This selecti/ity is the 3asic cause o. the highly characteristic spectrum o. each chemical
compound 6hich is, in turn, the reason .or the /alue o. spectroscopy as a means o. iden2
ti.ying atoms and molecules7 We shall return to the su3@ect o. selection rules 6ith some
eamples in Section %7-7,7
We might note here that, since energy and mass are related 3y '0uation (%7*7*+, the
conser/ation o. these t6o 0uantities should 3e considered together7 But this .act plays no
discerna3le role in the spectroscopy o. interest to chemists and 6e conLne our attention
here to conser/ation o. energy 6hich .orms the 3asis o. the most .undamental o. all the
selection rules1 the Bohr I 'instein condition7
,1)1% T$e 8o$r I Einstein #on/ition
Strange as it may seem to us today, 'insteinGs concept o. the light particle or photon
recei/ed little attention in the years immediately .ollo6ing its pu3lication in #$057 But in
#$#, the idea played a central role in BohrGs pre20uantum2mechanical theory o. the hydro2
gen atom (Sections 27-7# and 27-72+7 9a/ing 0uantised the or3ital angular momentum, and
hence the energy, o. his planetary electron, Bohr postulated that 6hen an electron changed
or3it it emitted or a3sor3ed the energy di..erence 3et6een the energy o. the initial, E
i
,
The 0uantum mechanics o. transition pro3a3ility 22-
and the Lnal, E
.
, states according to the e0uation1
E = |E
.
E
i
| = h>. !%.5.#"
Thus, i. the energy o. the photon is h>, as 'instein had proposed, '0uation (%757#+
is the e0uation o. energy conser/ation and determines the region o. the e2m spectrum
in 6hich each type o. atomic and molecular process is o3ser/ed spectroscopically7 To
appreciate the conser/ation o. other 0uantities, especially the most important o. them
angular momentum, 6e must eamine the interaction o. e2m radiation and matter in more
detail, and 6e do this in Section %7?7
An addition to the .undamental concepts associated 6ith conser/ation o. mass, energy
and angular momentum noted a3o/e, at least one other general /ie6 o. the selection
rules can 3e discerned7 A. 6e again consider e2m radiation as a 6a/e rather than as a
stream o. photons, 6e may en0uire as to ho6 the radiation actually interacts 6ith a
molecule7 What is the mechanism 3y means o. 6hich an e2m radiation 6a/e can change
the electron distri3ution in a molecule or induce a higher energy mode o. /i3ration in itJ
The QhandsG 6ith 6hich the e2m radiation QgraspsG the molecule are the oscillating electric
and magnetic Lelds7 The electric Leld, .or eample, can interact 6ith a permanent dipole
moment, i. one eists in a moleculeP the magnetic Leld can interact 6ith the magnetic
moment o. an electron, or o. a nucleus i. that nucleus has a magnetic moment7 These are
the concepts 6ith 6hich 6e shall see4 to understand the nature o. spectroscopic selection
rules 6hich apply in the indi/idual spectral regions7 An the net section o. this chapter 6e
set the scene 3y gi/ing a semi2classical description o. the interaction o. e2m radiation 6ith
matter7 An Section %7$ attention 6ill 3e dra6n to a purely 0uantum2mechanical theory o.
the interaction, 71ant1m electrodynamics7
,1* THE QUANTUM MECHANICS 26 TRANSITI2N !R28A8I5ITY
This section 6ill 3e one o. the more mathematical parts o. the 3oo4 and readers 6ho
6ould pre.er to lea/e it aside at present may do so i. they note care.ully the .ollo6ing
points, 6hich 6ill also ser/e as a guide .or those 6ho propose to 6or4 through the
material7
#7 We Lrst set up a 6a/e .unction that descri3es a system 6hich is changing in timeP i7e7
one 6hich is ma4ing a transition .rom an initial state ha/ing a 6a/e .unction
i
and
an energy E
i
to a Lnal state 6ith 6a/e .unction
.
and energy E
.
7
27 We recognise that such a 6a/e .unction has time2dependent and time2independent parts
and 6e .ocus our attention upon the .ormer7
,7 We disco/er that the com3ination o. the time2dependent part o. the 6a/e .unction
and the time2dependency o. the radiation (sin At +, acting o/er a Lnite period o. time,
- , results in a non2Kero interaction only 6hen the Bohr I 'instein condition o.
energy conser/ation is satisLed7 At must 3e emphasised that the Bohr I 'instein
condition is not introduced into the analysisP it arises 0uite naturally7
*7 This time2dependent part o. the pro3lem is common to all 3ranches o. spectroscopy
and the Bohr I 'instein condition there.ore represents a /ery .undamental and
6idely applica3le selection rule7
22% Spectroscopy
57 The time2independent part o. the pro3lem, ho6e/er, /aries 6ith the type o. spec2
troscopy in/ol/ed and does not ta4e the same .orm in all 3ranches o. the su3@ect7
We no6 attempt to ans6er the 0uestions1 9o6 does an electromagnetic 6a/e interact
6ith an atom or molecule and cause it to change its energy state 3y a3sor3ing energy
.rom the radiationJ What is the mechanism o. this process and ho6 does it gi/e rise to
selection rulesJ
With pro3lems such as the a3o/e in mind, 'r6in SchroM dinger .ormulated
t6o 0uantum2mechanical e0uationsP the time2independent and the time2dependent SchroM
dinger e0uations7 We ha/e already discussed and used the Lrst o. these e0uations in
Chapters 2 and ,7 At ta4es the .orm1
9

$
a
=
E
a
$
a
!%.?.#"
in 6hich $
a
is an eigen.unction o. the energy operator, 9

, 6ith eigen/alue E
a
7
9

$
a
are .unctions o. the spatial co2ordinates , y and K only7
The time2dependent e0uation ta4es the .orm1
and
ih
9


=
2(

D
!%.?.2"
Dt
9

is the same as in '0uation (%7?7#+, i is

!#", h is !lanc4Gs constant and the


simplest .orm o. is a product o. the $
a
.rom '0uation (%7?7#+ and a time2dependent
eponential term1

=
$
a
ep!

i2(E
a
t, h" !%.?.,"
We see that it is a .unction o. the three spatial co2ordinates (.rom $
a
+ and o. the time,
t 7 At is con/enient to simpli.y the a3o/e epression .or 3y noting that1
E = h> = hA,2( or A = 2(E, h !%.?.*"
6here A is an angular .re0uency measured in radians per second7
=sing '0uation (%7?7*+, can 3e 6ritten1
= $
a
ep!iA
a
t " !%.?.5"
An this simple .orm is an eigen.unction o. the time2dependent SchroM dinger
e0uation 6ith the eigen/alue E
a
7 But the most general .orm o. is a linear
com3ination o. .unctions o. the .orm1
= c
#
$
#
ep!iA
#
t " + c
2
$
2
ep!iA
2
t " + c
,
$
,
ep!iA
,
t " +
i7e71
=
a
c
a
$
a
ep!iA
a
t " !%.?.?"
6here c
a
are coe.Lcients 6hich tell us ho6 much o. each .unction $
a
ep!iA
a
t " there
is in 7 The energy o. a system descri3ed 3y such a general 6a/e .unction as is not
constant7 At changes 6ith time (Bo %72+, 6hich is @ust 6hat 6e re0uire .or a description
o. a spectroscopic transition7
An a3sorption spectroscopy 6e are normally particularly interested in a transition
3et6een @ust t6o states, an initial state,
i
, and a Lnal state,
.
, 6hich ha/e energies
o. E
i
and E
.
6ith E
i
P E
.
7 Then the 6a/e .unction 6hich descri3es all stages o. the
process
6here3y the system a3sor3s energy and goes .rom
i
to
.
during the time inter/al t = 0
to t = - is1
and

=
c
i
$
i
ep!

iA
i
t "
+
c
.
$
.
ep!

iA
.
t " !%.?.-"
at t = 01 =
i
= $
i
ep!iA
i
t " 6ith precise energy E
i
and c
i
= # c
.
= 0 at t
= - 1 =
.
= $
.
ep!iA
.
t " 6ith precise energy E
.
and c
i
= 0 c
.
= #
We see that the coe.Lcients, c, are also .unctions o. time and 6e shall use the change
in the /alue o. c
.

c
.
to trac4 the progress o. the transition .rom
i
to
.
7 At is clear
that
.or this process to ta4e place there must 3e some property o. the electromagnetic radiation
6hich lin4s the t6o states
i
and
.
7 Let us represent that property 3y an operator, V

,
6hich 6e 6rite is a product o. t6o parts, one a .unction o. the spatial co2ordinates only
and the other a .unction o. the time1
V

= V

!,y,K" V

!t " !%.?.%"
At 6ill also 3e con/enient to deLne the sym3ol 8
. i
as1
8
. i
$
.
|V

!,y,K"|$
i
ep!iA
.
t"|V

!t "| ep!iA
i
t " !%.?.$"
6hich 6ill ha/e a Lnite /alue .or an allo6ed transition7
We say that the e..ect o. the electromagnetic radiation is to pertur3 the systemP the
operator V

represents that pertur3ation7 This is epressed in 0uantum mechanics (see


Appendi *+ 3y 6riting a ne6 9amiltonian operator, 9

, .or the system as a sum o. the
original 9amiltonian, 9
0
, and the pertur3ation1
9

= 9
0
+ V

!%.?.#0"
The SchroM dinger e0uation 6hich descri3es the system under the inOuence o. the
per2 tur3ation is there.ore1
!9

0
+
V

"
=
ih

D
!%.?.##"
2( Dt
A. descri3es our simple t6o2state system ('0uation (%7?7-++ then su3stitution into
'0uation (%7?7##+ gi/es1
c
i
9
o
$
i
ep!iA
i
t" + c
.
9
o
$
.
ep!iA
.
t" + c
i
V

$
i
ep!iA
i
t" + c
.
V

$
.
ep!iA
.
t"
ih

D c
i D$
i =
2( Dt

$
i
ep!

iA
i
t"
+
c
i
Dt

ep!

iA
i
t"
D c
.
D$
. +
Dt

$
.
ep!

iA
.
t"
+
c
.
Dt

ep!

iA
.
t"
(%7?7#2+
;ote that in .orming D ,D t on the right2hand side o. the a3o/e e0uation the .unctions
to 3e di..erentiated ha/e 3een treated as products 3ecause the coe.Lcients, c, are also
.unctions o. time as 6e sa6 a3o/e7
Because o. '0uations (%7?72+ and (%7?7,+, the Lrst t6o terms on the le.t o. '0uation
(%7?7#2+ cancel the second and the .ourth on the right and the e0uation reduces to1
ih

D c
i
D c
.
c
i
V

$
i
ep!

iA
i
t"
+
c
.
V

$
.
ep!

iA
.
t "
=
2(
Dt

$
i
ep!

iA
i
t"
+
Dt

$
.
ep!

iA
.
t"
!%.?.#,"
c
.
A. 6e multiply each term o. '0uation (%7?7#,+, on the le.t, 3y $
.
ep!iA
.
t"| and
integrate o/er all spatial co2ordinates and time 6e ha/e1
c
i
$
.
ep!iA
.
t"|V

|$
i
ep!iA
i
t" + c
.
$
.
ep!iA
.
t"|V

|$
.
ep!iA
.
t"
ih

D c
i
D c
. =
2( Dt

$
.
ep!

iA
.
t"
|
$
i
ep!

iA
i
t"
+
Dt

$
.
ep!

iA
.
t"
|
$
.
ep!

iA
.
t"

!%.?.#*"
An this *ra+;et notation, 6hich 6e ha/e used 3e.ore in Chapter ,, the PR means
integration o/er all the co2ordinates in the operator, i7e7 , y, K and t 7 ;ote that the
eponential term on the le.t2hand side o. each 3rac4et is re0uired 3y 0uantum mechanics
to 3e the comple con@ugate (i +iP Appendi %+ o. $
.
ep!iA
.
t "7 9o6e/er, this
is not 6ritten eplicitly, rather it is im%lied 3y the *ra ( |+7 The Lrst integration on the
right2hand side o. '0uation (%7?7#*+ gi/es Kero 3ecause the .unctions $
i
ep!iA
i
t " and
$
.
ep!iA
.
t " are orthogonal to each other7 The integration o. the second term gi/es one
3ecause $
.
ep!iA
.
t " is normalised7 Simpli.ying the notation using '0uation (%7?7$+ and
rearranging 6e o3tain '0uation (%7?7#*+ in the compact .orm1
D c
.
Dt
=
2(
ih
{
c
i
8
. i
+
c
.
8
..
}
!%.?.#*a"
At the onset o. the pertur3ation c
i
= # and c
.
= 0 so that1
D c
.
Dt
=
2(
8
. i
!%.?.#5"
ih
This e0uation is an epression .or the change o. c
.
6ith time7 By monitoring its /alue
6e can .ollo6 the change in the system 6ith time under the inOuence o. the pertur3ation7
Suppose that the pertur3ation lasts .or a time - 7 The /alue o. c
.
at the end o. that time,
c
.
-
, can 3e .ound 3y e/aluating the integral1
-
-
= D c
.
=
0
-
2(

ih
0
8
. i
Dt !%.?.#?"
A. 6e recall that the deLnition o. 8
. i
('0uation (%7?7$++ in/ol/es integration o/er the
spatial co2ordinates , y and K, then '0uation (%7?7#?+ re0uires integration o/er all spatial
and time /aria3les and it is con/enient to separate the integrations o/er space and time7
This is 6hy 6e ha/e 6ritten 8
. i
as a product o. a space2dependent and a time2dependent
part in '0uation (%7?7$+, 6hich 6e repeat here .or con/enience1
8
. i
$
.
|V

!,y,K"|$
i
ep!iA
.
t"|V

!t "| ep!iA
i
t " !%.?.$"
The Lrst term, the time2independent term, is 0uite speciLc to the type o. spectroscopy
and is not the same, .or eample, .or in.rared and ;C: spectroscopy7 We there.ore lea/e
the time2independent term aside .or the moment and consider it again in Section %7-7
The time2dependent term, on the other hand, is eactly the same in all cases and it 6ill
there.ore 3e considered here in the general discussion7 Com3ining the t6o eponential
.unctions (remem3er that the *ra implies the comple con@ugate o. the .unction 6ritten
inside it+ the integral can 3e 6ritten1
-
0
6here A = A
.
A
i
7
-
epZi!A
.
A
i
"t \V

!t " dt
0
epZi At \V

!t " dt !%.?.#-"
Since ep!i At " = cos! At " + i sin! At " (Bo ,7# and Appendi %+, 6e see that
the eponential .unction is a .unction 6hich oscillates in time and the integral o. such
a .unction 6ill normally contain a large num3er o. e0ual and opposite contri3utions
6hich 6ill sum to Kero (Digure %7-(a++7 We there.ore re0uire that V

!t " should also 3e
an
oscillating .unction 6hich, i. suita3ly chosen, cancels the oscillations o. the eponential
term gi/ing a non2Kero /alue .or the integral7 The electric Leld o. a 3eam o. light seems a
good choice 3ecause it has the re0uired oscillatory character and the presence o. the Leld
6ill change the potential energy o. the charged particles o. 6hich atoms and molecules
are .ormed7 We there.ore in/estigate the .unction1
V

!t " = E
0
sin At = E
0
{ep!iAt " ep!iAt "},2i !%.?.#%"
3ecause it is o. the .orm 6hich 6e ha/e used earlier to descri3e the 6a/es o. electro2
magnetic radiation7 Su3stituting '0uation (%7?7#%+ into '0uation (%7?7#-+ our integral o/er
time 3ecomes1
-
E
0
epZi At \ sin At dt =
0
-
E
0

2i
0
epZi At \ {ep!iAt " ep!iAt "} dt
i
- -
i
E
0

=
2i
i
0
ep{i! A + A"t } dt
0
ep
{
i! A

A"t
}
dt
i
(%7?7#$+
since E
.
R E
i
A
.
R A
i
and A R 07 There.ore, the argument o. the Lrst
eponential term is al6ays large gi/ing a rapidly oscillating .unction 6hich integrates to a
/ery small 0uantity (Digure %7-(a++7 But the argument o. the second eponential can 3e
small and
(a+
(3+
(c+
6 + 6 >> 0
6 6 0
6 6 = 0
t = 0
6ig;re ,1+ The integral in '0uation (%7?7#$+
t = -
2
is, in .act, Kero 6hen A = A7 There.ore, the second term in the integral is slo6ly
/arying in the .re0uency range A A and it can contri3ute to a signiLcant /alue o.
the integral (Digure %7-(3++7 The maimum contri3ution 6ill 3e o3tained 6hen A = A
since the eponential .unction is then ep!0" = # 6hich sho6s no Ouctuation 6ith time,
(Digure %7-(c++7 Thus the maimum interaction o. the molecule 6ith the radiation arises
6hen1
A = A = A
.
A
i
or (using '0uation (%7?7*++ in terms o. .re0uency and energy, 6hen1
2(> = !2(, h" !E
.
E
i
" or E
.
E
i
= h>
We ha/e o3tained the Bohr I 'instein or energy conser/ation rule 6ithout any
mention o. energy conser/ation7 This result may 3e ta4en as conLrmation, i. such is
needed, o. 'insteinGs proposal that the energy o. an electromagnetic 6a/e could 3e
epressed in terms o. photons o. energy h>7 ;ote that the argument 6ould ha/e 3een
made in eactly the same 6ay, and 6ith eactly the same result, had 6e 3een
considering stimulated emission .or 6hich E
.
P E
i
A
.
P A
i
and A P 07 Then it 6ould
ha/e 3een the Lrst term o. '0uation (%7?7#$+ 6hich 6as the important one7
;o6 6e can complete our analysis 3y carrying out the integration, 6hich is 0uite
simple7 ;eglecting the Lrst term on the right in '0uation (%7?7#$+ 6e ha/e1
-
E
0

E
0

ep
{
i! A

A"t
}

-

2i
0
ep
{
i! A

A"t
}
dt
=
2i

i! A A"
0
E
0
Zep{i! A A"- } #\ =
2! A

A"
We ha/e e/aluated the integral in '0uation (%7?7#?+ to o3tain c
.
-
, the /alue at t = - o.
the 6a/e .unction coe.Lcient c
.
deLned in '0uation (%7?7-+7 Since in 0uantum mechanics,
pro3a3ility is determined 3y the product o. the 6a/e .unction 6ith its comple con@ugate,
the time2dependent part o. the transition pro3a3ility, W !t ", is proportional to the
product o. this result and its comple con@ugate1
W !t " =
E
0
Zep{i! A A"- } #\
2! A

A"

E
2
E
0
Zep{i! A A"- } #\
2! A A"
0
Zep{0} + # ep{i! A A"- } ep{i! A A"- }\ =
*! A

A"
2
E
2 2 2 #
0
Z2 2 cos{! A A"- }\ =
*! A

A"
2
=
E
0
Zsin
{
2
! A

A"-
}
\
! A

A"
2
This important .unction is sometimes 6ritten in the .orm1
E
2 2 #
W !t " =
0
sin
{
2
! A

A"-
}
*
{
#
! A

A"
}
2
!%.?.20"
W !t " is plotted against ( A A+ .rom ,(, - to +,(, - 6ith E
0
= # and - = 2
in Digure %7%7 At is interesting to note that this .unction 6as Lrst o3tained theoretically
The ;ature o. the Time2Andependent Anteraction

$
.
|
V
j
!,y,K"
|
$
i

2,,
0
2
2
T
r
a
n
s
i
t
i
o
n

p
r
o
3
a
3
i
l
i
t
y
#72
#70
07%
sin
2
Zc (6 6+- \
(6 6+
2
07?
07*
072
070
,p 2p p +p +2p +,p
#0 5 0 5 #0
6 6
6ig;re ,1, Graph o. the .unction o. '0uation (%7?720+
in the early #$,0s, 3ut no eperimental con.ormation o. its peculiar .orm 6as a/aila3le
until #$-2 6hen it 6as o3ser/ed directly in a molecular 3eam eperiment7
,
When the Dunction (%7?720+ is multiplied 3y the s0uared, time2independent, part o. the
interaction | $
.
|V

!,y,K"|$
i
|
2
and the .actor !2(, ih" !2(, ih" .rom '0uation (%7?7#?+,
6e ha/e as our Lnal epression .or the transition pro3a3ility 3et6een the t6o states
i
and
.
1
W !,y,K t " = E
2

*(
2
h
2
| $
.
|V

!,y,K"|$
i
|
2

sin
2
{
#
! A A"- }
*
{
#
! A

A"
}
!%.?.2#"
2
The time2independent .unction is the origin o. all spectroscopic selection rules, apart
.rom the Born I 'instein condition, and conse0uently it is responsi3le .or much o. the
detail in the spectroscopic in.ormation 6e o3tain .rom molecules7 An the net section 6e
eamine its particular .orm .or three ma@or 3ranches o. chemical spectroscopy I electronic,
in.rared and nuclear magnetic resonance7
,1+ THE NATURE 26 THE TIME9IN3E!EN3ENT
L
INTERACTI2N $
"
k*
)
!x< 0< M"k$
i

To proceed .urther 6ith our in/estigation o. the interaction o. radiation 6ith matter, 6e
must consider the eplicit .orm 6hich the time2independent part o. the interaction, char2
acterised 3y the operator V

!,y,K", ta4es in the case o. the indi/idual spectroscopies7


Though all 3ranches o. spectroscopy ha/e made important contri3utions to chemical
4no6ledge, electronic (ultra/iolet2/isi3le, =8 I 8AS+, in.rared (A:+ and nuclear
magnetic resonance (;C:+ spectroscopy ha/e played 3y .ar the greatest role in this
contet7 Dur2 thermore, these three 3ranches o. the su3@ect are used much more
etensi/ely e/ery day in e/ery chemical research la3oratory and accordingly 6e here
conLne our attention to these three only7
]
Comment on notation1 An this section 6e need to distinguish 3et6een 6a/e .unctions 6hich relate to di..erent aspects o. a
molecular energy stateP in particular 6e 6ish to distinguish 3et6een electronic and /i3rational 6a/e .unctions7 To ma4e this
possi3le 6e no6 6rite i and . as superscripts lea/ing the su3script position /acant .or later use7
total
total
total
|
"

|
$
= G
G
elec
G
An the case o. =8 I 8AS and A: spectroscopy it is the electric Celd, E, o. the
elec2 tromagnetic radiation 6hich interacts 6ith a changing electric dipole moment, ", in
the molecule and through this interaction causes the electronic or /i3rational state (or 3oth+
o. the molecule to change .rom an initial state $
i
to a Cnal state $
.
7 An ;C:
spectroscopy a magnetic nucleus 6ith magnetic moment, T, changes its orientation 6ith
respect to the applied, static magnetic Leld, B
0
, 3ecause o. its interaction 6ith the
magnetic Celd, B
#
, o. the electromagnetic radiation7 The .orm o. these t6o types o.
interaction is /ery similar1
=8 I 8AS and A:1 electric dipole interaction energy
=
E

"
f
$
.
|E "

|$
i
= E $
.
|"

|$
i
!%.-.#"
;C:1 magnetic dipole interaction energy = B
#
T
$
.
|B
#
T |$
i
= B
#
$
.
|T |$
i
!%.-.2"
These are simply the classical e0uations .or the dipole2Leld interaction energy7 The
QdotG indicates the scalar product o. t6o /ectors 6hich is deLned 3y the e0uation1
A 8 = A

B

+ A
y
B
y
+ A
K
B
K
so that1
E $
.
|"

|$
i
= E

$
.
|5


|$
i
+ E
y
$
.
|5

y
|$
i
+ E
K
$
.
|5

K
|$
i

We see that in order .or there to 3e an interaction 3et6een the electric (magnetic+ Leld
o. the radiation there must 3e a matri element o. the electric (magnetic+ dipole moment
operator in the same direction7 At is this 6hich gi/es spectroscopy 6ith polarised light the
a3ility to pro/ide in.ormation a3out directions 6ithin a molecule7
To calculate the intensity o. a spectral line, 6e must e/aluate the a3o/e matri elements
o.
"

and T .or the spectroscopies in 0uestion7 An the case o. =8 I 8AS and A:


spectroscopy
6e re0uire the electric dipole moment,

$
.
|
"

|
$
i

, associated 6ith the transition and in
the case o. ;C: spectroscopy the corresponding magnetic moment7 We Lrst consider the
=8 I 8AS and A: case7
,1+1% T$e transition /ipole moment
An Appendi $ 6e sho6 that the transition dipole moment, "
i.
, .or a transition .rom an
initial state, $
i
, to a Lnal state, $
.
, is gi/en 3y the e0uation1
"
i.
= $
.
i
total
.
elec
.
/i3
|"

|G
i i
/i3
!%.-.,"
"
i.
is the transitory dipole moment generated 6hen the molecule changes its state
and, in a 6a/e23ased /ie6 o. the interaction o. radiation and matter, it is the QhandleG 3y
means o. 6hich the oscillating electric Leld o. the radiation is a3le to couple 6ith the
molecule7
An deri/ing '0uation (%7-7,+ the Born I "ppenheimer approimation (Section ?7,+
has 3een used to epress the total 6a/e .unction as a product o. an electronic and a
/i3rational .unction1
$
total
!,F"
=
G
elec
!,F"

G
/i3
!F" !%.-.*"
f
;ote that this epression .or the interaction assumes that the 6a/elength o. the radiation is much greater than the dimensions
o. the atom or molecule7 Dor e/eryday chemical spectroscopy this assumption is /ery 6ell @ustiLed7
/i3
| G
elec
| G
/i3 /i3
elec
elec
elec
and G
4
4
4
/i3 /i3


4
elec
= G
/i3
= G
6here the presence o. 3oth electronic (+ and nuclear (F+ co2ordinates .ollo6ing G
elec
reminds us o. the .act that the electronic 6a/e .unction depends upon the positions o.
the nuclei as 6ell as upon those o. the electrons7 Dor a discussion 6hich includes the
rotation o. the molecule see Section #0757 ZAn '0uation (%7-7,+ the (F+ and (,F+ ha/e
3een dropped to simpli.y the notation7\
'0uation (%7-7,+ may 3e 6ritten in the .orm1
"
i.
= G
.
.
elec
|"

| G
i i
/i3
= G
.
|"
F
!e
.
e
i
"| G
i
!%.-.5"
in 6hich "
F
(e
.
e
i
+ is the result o. e/aluating the integral G
.
|"

| G
i
o/er the elec2
tronic co2ordinates .or a particular nuclear conLguration represented 3y F7 The presence
o. the sym3ols F, e
.
and e
i
in "
F
(e
.
e
i
+ again reminds us that the result o. the integra2
tion depends upon the t6o electronic 6a/e .unctions in/ol/ed, G
. i
elec
, and the
particular nuclear co2ordinates chosen, F7
But 6e must allo6 .or the dependence o. "
i.
upon the nuclear conLguration and
there.ore to proceed .urther 6e epress "
F
(e
.
e
i
+ as a sum o. t6o terms1
,;?
"
F
!e
.
e
i
"
=
"
0
!e
.
e
i
"
+

&
;
"

!e
.
e
i
" !%.-.?"
4=#
The Lrst term is the /alue o. "
F
(e
.
e
i
+ at the e0uili3rium nuclear conLguration7 An
the second term, "

!e
.
e
i
" D "
0
!e
.
e
i
",D &
4
, the deri/ati/e o. "
F
(e
.
e
i
+ 6ith respect to
&
4
at
the e0uili3rium conLguration7 &
4
is the 4
th
normal co2ordinate7 The motion o. the atoms
o. a molecule along a normal co2ordinate is a /i3ration 6hich is an eigen.unction o. the
/i3rational 9amiltonian o. the molecule (see Section #07-7#+7
Thus, &
4
"

(e
.
e
i
+ is the change in the /alue o. "
F
(e
.
e
i
+ 6hen the nuclear
conLguration di..ers .rom its e0uili3rium /alue 3y a displacement along the normal
co2ordinate &
4
7
The actual /alue o. that displacement, G
.
|&
4
| G
i
, 6ill enter the calculation 6hen
the integration o/er the /i3rational 6a/e .unction is per.ormed7 The 3asic assumption
o. this epansion is that the Lrst term is /ery much larger than the second 6hich, in
turn, is /ery much larger than any .urther terms, e7g7 &
@
&
4
"

"

(e
.
e
i
+ or &
4
2
"

4
(e
.
e
i
+7
@ 4
An Section %7-72 6e shall Lnd that this assumption is 6ell @ustiLed7 '0uation (%7-75+ can
no6 3e re6ritten in the .orm1

,N

?
"
i.
=
G
.
|
"
0
!e
.
e
i
"
|
G
i
+
G
.


& "

!e
.
e
i
"

G
i
/i3
/i3
/i3

4 4

;=#
/i3
=
G
.
|
G
i
,;?

"
0
!e
.
e
i
"
+


G
.
|
&
|
G
i

"

!e
.
e
i
" (%7-7-+
/i3 /i3
4=#
/i3 4 /i3 4
We can ta4e "
0
(e
.
e
i
+ and "

(e
.
e
i
+ outside the integration o/er the /i3rational
.unctions implied 3y 3ecause they are 3oth constantsP though they do, o. course,
ha/e units7
'0uation (%7-7-+ is a /ery general epression 6hich applies to any molecule, and 6e can
recognise in it the .ollo6ing three important special cases7
Case /: G
.
i
elec
3ut G
. i
/i3
An this case there is a change o. /i3rational state 3ut no change o. electronic state, i7e7 6e
ha/e an in.rared transition7 The Lrst term on the right in '0uation (%7-7-+ is Kero 3ecause
the t6o di..erent /i3rational 6a/e .unctions 3elong to the same electronic state and are
/i3 /i3
/i3
= G
@
@ 4
@
@
@
@
elec
= G
/i3
= G
or G
= G
/i3
= G
/i3
| G
elec
= G
there.ore orthogonal7 Thus, the transition dipole moment is gi/en 3y the second term7
The /i3rational states, G
.
and G
i
, can 3e 6ritten as products o. normal /i3rational
modes (Section #07-+ 3ut 3ecause G
. i
/i3
the t6o products 6ill not 3e identical7 Let
us eamine the possi3ility that a particular /i3rational mode, &
@
say, can lose or gain
0uanta to go .rom G
i
(&

+ in G
i
to G
.
(&

+ in G
.
6hile the num3ers o. 0uanta in all
@ /i3 @ /i3
other /i3rational modes remain unchanged7 The second term in '0uation (%7-7-+ is then1
,;?
"
i.
=


G
.
|
&
|
G
i

"

!e
i
e
i
"
4=#
,;?
/i3 4 /i3 4
=
4=#
G
.
!&
#
"G
.
!&
2
" . . . G
.
!&

" . . . G
.
!&
,;?
"
|
&
4
|
G
i
!&
#
"G
i
!&
2
" . . . G
i
!&

" . . . G
i
!&
,;?
" "

!e
i
e
i
"
=
G
.
!&
#
"
|
G
i
!&
#
"

. . .

G
.
!&

"
|
&
|
G
i
!&

"

. . .

G
.
!& "
|
G
i
!& "

"

!e
i
e
i
"
@ @ @ ,;? ,;

? @
=
G
.
!&

"
|
&
|
G
i
!&

"

"

!e
i
e
i
" (%7-7%+
@ @ @ @
The sum o/er 4 reduces to a single term in the penultimate line o. '0uation (%7-7%+
since it is only 6hen 4
=
@ that 6e do not ha/e the integral

G
.
!&

"
|
G
i
!&

@
"

6hich is
Kero 3ecause 6e ha/e assumed that the same mode, &
@
, has di..erent 0uantum num3ers in
G
.
(&

+ and G
i
(&

@
+7 The simpliLcation in the last line is a conse0uence o. the .act that all
the normal /i3rational modes o. the same electronic state are orthogonal and normalised1
G!&
m
"|G!&
n
" = )
mn
!%.-.$"
The result, '0uation (%7-7%+, sho6s that i. an in.rared transition in the normal mode
&
@
is to 3e allo6ed there must 3e a change o. dipole moment associated 6ith that /i3ra2
tion, i7e7 "

!e
i
e
i
" = 07 The in.rared selection rule is em3odied in the multiplying .actor

G
.
!&

"
|
&
|
G
i
!&

@
"

, 6hich is e/aluated and discussed in Section #0757 At 6ill 3e su.L2
@ @
cient here i. 6e say that it is Kero unless the /i3rational 0uantum num3ers o. the 6a/e
.unctions G
.
!&

" and G
i
!&

@
" di..er 3y #7
Case 2: G
.
i
elec
and "
0
!e
.
e
i
" = 0P G
. i
/i3
.
/i3
i
/i3
This is the case o. an allo6ed electronic transition Z"
0
!e
.
e
i
" = 0\, 6hich may 3e accom2
panied 3y a simultaneous change o. /i3rational state, G
. i
/i3
, or 3y no change,
G
. i
/i3
=
G
/i3
7 Both terms in '0uation (%7-7-+ contri3ute to the transition dipole moment
3ut, .or the reasons gi/en a3o/e, the second term is neglected in comparison 6ith the
Lrst term 6hich is /ery much larger7 Thus, the transition dipole moment is gi/en 3y1
"
i.
= G
.
i
/i3
"
0
!e
.
e
i
" !%.-.#0"
We see that the transition dipole moment .or the /i3ronic (vi*ronic = product o. /i3ra2
tional and electronic states+ transition as a 6hole is determined 3y the electronic transition
dipole moment calculated at the e0uili3rium internuclear distance multiplied 3y the o/er2
lap o. the /i3rational 6a/e .unctions o. the initial and Lnal states7 The t6o /i3rational
.unctions are not orthogonal 3ecause G
. i
elec
7 This result 6as Lrst deri/ed 0uantum2
mechanically 3y 'd6ard =hler Condon (#$02 I #$-*+, 3ut James Dranc4 (#%%2 I #$?*+
had
o3tained it earlier using classical theory7 Accordingly, it is 4no6n as the Dranc4 I Condon
elec
= G
/i3
= G or G = G

4
4
elec
and G
elec
elec
elec
G
elec elec
4
principle7 With its aid e/en 0ualitati/e analysis o. the .orm o. the /i3rational structure o.
an electronic a3sorption 3and can gi/e us /alua3le in.ormation a3out the relati/e shapes
o. the ground and ecited state potential energy cur/es7 This is illustrated in Bo %7,7
The concept is also help.ul in descri3ing the /i3rational structure o. .or3idden electronic
transitions 6hich are allo6ed 3ecause o. molecular /i3rations, as 6e shall see 6hen 6e
consider Case ,7
Case 6: G
.
i
elec
and "
0
!e
.
e
i
" = 0P G
. i
/i3
.
/i3
i
/i3
This is the case o. a .or3idden electronic transition Z"
0
!e
.
e
i
"
=
0\, 6hich may 3e 6ea4ly
o3ser/ed 3ecause o. the presence o. the second term in '0uation (%7-7-+ 6hich deter2
mines 6hether transitions ha/ing "
0
!e
.
e
i
" = 0 occur as a result o. molecular /i3ra2
tions7 The /i3rational states may 3e epanded in terms o. the normal co2ordinates as
in '0uation (%7-7%+ gi/ing1
,;?
"
i.
=


G
.
|
&
|
G
i

"

!e
.
e
i
"
,;?
4=#
/i3 4 /i3 4
=
4=#

G
.
!&
#
"
|
G
i
!&
#
"

. . .

G
.
!&
4
"
|
&
4
|
G
i
!&
4
"

. . .

G
.
!&
,;
?
"
|
G
i
!&
,;?
" "

!e
.
e
i
"
!%.-.##"
since the t6o sets o. normal modes 3elong to t6o di..erent electronic states

G
.
!&
n
"
|
G
i
!&
n
"
=
#7 But such integrals are also unli4ely to 3e Kero, unless the
t6o electronic potential energy cur/es are /ery di..erent7 ;e/ertheless, the /i3rational
contri3ution to the intensity o. the .or3idden electronic spectral 3and can 3e e/aluated,
though this is not normally done using '0uation (%7-7##+7 The /alue o.
"

is re0uired
and the usual method employs pertur3ation theory (Appendi *+ to calculate the degree
to 6hich the /i3rations, 3y changing the shape o. the molecule, mi G
. i
elec
6ith
other electronic states7 An most cases o. practical interest G
i
is the ground state, 6hich
does not mi signiLcantly 6ith other states since they are so much higher in energy7
The miing is there.ore conLned to the miing o. G
.
6ith near3y ecited states7 The
result o. the miing is that the transition is no longer purely G
i .
elec
3ecause there
are some states among those ne6ly mied into G
.
to 6hich transitions .rom G
i
are
allo6ed7 An this 6ay the Q.or3iddenG transition ac0uires some intensity, 6hich it is said
to ha/e Q3orro6edG or QstolenG .rom one or more allo6ed transitions7
A. the potential energy cur/es o. the t6o electronic states are 0uite similar in .orm and
di..er only in energy, 6hich may 6ell 3e the case .or the ecitation o. one electron in a
large molecule, then the /i3rational eigen.unctions o. the t6o states 6ill 3e similar also7
Then, to a good approimation,

G
.
!&
n
"
|
G
i
!&
n
"
=
# and the ma@or contri3utions to the
transition dipole moment .rom each allo6ing /i3ration 6ill 3e o. the .orm1
G
.
!&
4
"|&
4
|G
i
!&
4
" "

!e
.
e
i
"
An Section #075 it is sho6n that the integral G
.
!&
4
"|&
4
|G
i
!&
4
" is Kero unless the
/i3rational 0uantum num3ers associated 6ith G
.
(&
4
+ and G
i
(&
4
+ di..er 3y #7 There.ore,
6here the electronic energy sur.aces o. the ground and ecited electronic states are similar,
6e anticipate that the /i3rational Lne structure o. a .or3idden electronic transition 6ill
correspond predominantly to changes o. # in the /i3rational 0uantum num3ers o. the
allo6ing /i3rations7 The allo6ing /i3rations are e..ecti/e 3ecause they change the shape
o. the moleculeP lo6ering its symmetry7 At is common to Lnd that the Lrst pea4 due to
an allo6ing /i3ration is .ollo6ed 3y a series o. pea4s in 6hich the allo6ing /i3ration
and an increasing num3er o. 0uanta o. a totally symmetric /i3ration are simultaneously
ecited7 Such a series o. 3ands is 4no6n as a %rogression7
Three .urther remar4s should 3e made 3e.ore 6e lea/e the long and complicated su3@ect
o. transition dipole moments7
#7 '0uation (%7?7#2+ sho6s that the intensity o. a transition 3et6een t6o states is pro2
portional to the s71are o. the transition dipole moment 3et6een them or, in the e/ent
that the transition dipole moment is a comple 0uantity, the product o. the transition
dipole moment and its comple con@ugate7
27 A similar analysis can 3e made 6ith respect to transitions stimulated 3y the magnetic
Leld o. the light, and 6e shall use this 6hen 6e come to consider an ;C: transition7
,7 An the case o. the #s 2p transition o. the hydrogen atom .or eample, though the
0uantum mechanical epression is 0uite clear, it is di.Lcult not to as4 ho6 the process
o. interaction 3et6een the light 6a/e and the spherically symmetrical atom Qgets
startedG7 Where is the dipole 6hich pro/ides the Lrst means o. interaction .or the e2m
6a/eJ An ans6er 6e may note that, since the nucleus and the electron are particles,
the atom is only spherically symmetrical 6hen the positions o. the nucleus and the
electron are a/eraged o/er some Lnite period o. timeP at any instant in time the atom
is a dipole7 A .urther eamination o. the conse0uences o. the time2dependency o. the
hydrogen2atom 6a/e .unctions can 3e .ound in Bo %727
An alternati/e, Qmore classicalG /ie6 o. the pro3lem is the .ollo6ing7 When light
passes through a transparent medium it does interact 6ith the medium e/en though it
is not a3sor3edP 6e 4no6, .or eample, that its /elocity is changed7 9o6e/er, 6hen
the .re0uency o. the light .ulLls the Born I 'instein condition, the pre/iously
limited response o. the electrons is much magniLed and a condition o. resonance is
esta3lished 6here3y electrons can a3sor3 the light energy and change their energy
states7 An terms o. the old analogy, a column o. soldiers marching o/er a 3ridge 6ill
certainly cause the 3ridge to sha4e 3ut 6ill do nothing more i. they are not all in
step7 9o6e/er, i. they are in step and the .re0uency o. their step matches a natural
/i3rational .re0uency o. the 3ridge, the 3ridge may oscillate much more /iolently
than is sa.e7 At 6as a phenomenon o. this type, caused 3y normal pedestrians
rather than soldiers, 6hich necessitated structural modiLcations to the Cillennium
Bridge o/er the :i/er Thames in London7 At appears that there 6as a remar4a3le t6o2
6ay process in 6hich the oscillations o. the 3ridge caused 3y the crossing
pedestrians induced in those same people a synchronised stepping .re0uency 6hich
increased the oscillation o. the 3ridge still .urther7
,1+1& T$e relatiAe intensities o" UV I VIS< IR an/ NMR transitions
Armed 6ith the a3o/e results 6e can proceed to eamine the simplest eample o. an
electronic transition1 the #s 2p transition o. the hydrogen atom7 A. 6e select as our
Lnal state the $
2pK
then the transition moment 6hich 6e re0uire is1
" = e $
2pK
|r|$
#s
= e $
2pK
||$
#s
+ e $
2pK
|y|$
#s
+ e $
2pK
|K|$
#s
!%.-.#2"
!
,
/i3 /i3
G
/i3
*
2
and e/aluation o. the three integrals sho6s that only the last gi/es a /alue that is not
Kero7 A. 6e choose $
2p
or $
2py
as our 2p or3ital then the matri elements containing the
operators and y respecti/ely 3ecome the non2Kero 0uantities in '0uation (%7-7#2+7 All
three contri3utions to " are e0ual since the three aes are e0ui/alent7 We shall e/aluate
the last term, "
K
, 3y ta4ing epressions .or the t6o hydrogen 6a/e .unctions (in atomic
units, Appendi #+ .rom Appendi 5 and replacing K 3y r cos # in order to ha/e all our
0uantities in polar co2ordinates7 :ecalling (Appendi -+ that the /olume element in polar
co2ordinates is r
2
sin # dr d# d$, 6e ha/e1
e



(

2(

r ep

r

cos #

r cos #

ep!

r"r
2
sin # dr d# d$
5
N
=
* 2( 0 0
e

0
2

,r

(

2(
=
2( 0
r
*
ep
2
dr cos
2
# sin # d# d$
0 0
(
e

=
2 0
r
*
ep

,r

dr
2
0
cos
2
# sin # d#
e

r
*
ep

,r

dr =
e 2*

= 0.-**$,? au
=
, 2 0
2
, 2
2
"
5
Thus, "
2
=
0.55*$ and "
2
=
,

"
2
=
#.??*% atomic units7 Con/erting .rom atomic
K K
to SA units 6e Lnd that a dipole moment o. 07-**$,? au = ?.,#5% #0

,0
C m so that the
2p transition dipole moment o. hydrogen is ,$.%%$ #0

?0
C
2
m
2
,
6hich agrees eactly 6ith the eperimental /alue7 This is a /ery satis.ying result in that
it conLrms that the 0uantum mechanical method o. calculating transition pro3a3ilities is
correct7 But 6e should not 3e lulled into a .alse sense o. security7 =ni0uely in the case o.
one2electron atoms, 6e ha/e etremely accurate alge3raic 6a/e .unctions at our disposal
.or calculations o. this type7 As soon as 6e mo/e to multi2electron atoms, and a fortiori
to molecules, the interelectronic repulsion drastically reduces the 0uality o. the a/aila3le
6a/e .unctions (see Chapter 5+ and agreement 6ith eperiment deteriorates rapidly7 Dor
a small molecule such as ethene agreement to 6ithin a .actor o. t6o or three is o.ten as
much as 6e can hope .or7
9o6e/er, our purpose here is not to o3tain accurate theoretical intensities 3ut rather
to ha/e some insight into their relati/e /alues in the =8 I 8AS, A: and ;C:
spectral regions7 There.ore, 6e do not consider possi3le reasons .or discrepancies
.urther 3ut go
on to consider a typical A: transition, the .undamental v
=
0 to v
=
# transition o. the
hydrogen chloride (9Cl+ molecule7
We ha/e to e/aluate the 'pression (%7-7%+, 6hich is a product o. G
.
|r|G
i
(r is the
only normal co2ordinate o. a diatomic molecule+ and the rate o. change o. the molecular
dipole moment 6ith 3ond length, "

(e

e+, at the e0uili3rium 3ond length, r
e
7 =sing data
.rom Bo #072 6e Lnd1
.
/i3
|r|G
i
#
=
!h,%(
2
T>"
2 =
-.5$ pm.
A. 6e assume that the charge distri3ution does not change 6ith 3ond length .or small
amplitude /i3rations a3out r
e
, then the change in dipole moment 6ith 3ond length depends
only upon the change o. 3ond length, and the rate o. change o. dipole moment 6ith
2
2
3ond length may 3e o3tained 3y di/iding the .ormer (,.?- #0

,0
C m+ 3y the latter
(#2-75 pm+1
6hence1
"

D "
0
,D : = ,.?- #0

,0
,#2-.5 #0

#2
= 2.%% #0

20
C
" = -.5$ 2.%% #0

,2
= 2.#$ #0

,#
C m "
2
= *.-% #0

?2
C
2
m
2
The 3est eperimental estimate o. " is 2.#% #0

,#
C m gi/ing a much closer agree2
ment 3et6een eperiment and our theoretical /alue than 6e ha/e any right to epectU
;ote that the /alue o. the s0uare o. the transition dipole moment, and hence the
intensity, .or a typical strong electronic transition is some .our orders o. magnitude
greater than that o. a strong in.rared transition7 This @ustiLes the assumption underly2
ing '0uation (%7-7#0+ and raises the 0uestion as to 6hy it should 3e so7 The essential
reason is that in an electronic spectral transition the transition dipole moment in/ol/es
the electrons directly, and they each carry a large charge7 An in.rared spectroscopy the
transition dipole moment depends upon a change o. dipole moment, 6hich depends upon
the differences in the distri3ution o. electronic and nuclear charge in the molecule7 The
di..erence in the intensities o. =8 I 8AS and A: 3ands has an important
eperimental conse0uence7 An.rared a3sorption spectra can .re0uently 3e measured on
samples o. pure su3stance 6hereas =8 I 8AS eperiments almost al6ays re0uire dilution
o. the sample in a suita3le sol/ent or inert matri7
Dor the ;C: case 6e shall again ta4e a simple eample and consider the magnetic
resonance o. a proton, 6hich can ta4e up t6o orientations to an applied, static magnetic
Leld7 A. 6e assume the con/entional eperimental set2up 6ith the static magnetic Leld, B
0
,
orientated along the K2direction and the oscillating radio .re0uency Leld, /
#
, along the
2direction, then the orientation o. lo6er energy has &
:
= +
#
and the higher energy ori2
entation has &
:
=
#
so that .or a3sorption o. radiation 6e must e/aluate (see Chapter $
.or the relation T

= N h` :


"1
/
#

$
.
|
T


|
$
i

/
#

m
:
= |
T


|
m
:
= +
# #
2 2
=
/
#

#
|
N h
`
:

| +
#
=
/
#
N h
`

#
|
:

| +
#
=
/
#
N
#
h
`
(%7-7#,+
2 2 2 2 2
"n inserting the /alue o. the magnetogyric ratio o. the proton (N = 2?.5-2 #0
-
rad
T

#