CHEM 342. Spring 2002. Problem Set #5. Mortimer Chapters 17, 1. !ns"ers.

Born-Oppenheimer Approximation
1. #hat is the main ass$mption o% the &orn'(ppenheimer appro)imation*
+he &orn'(ppenheimer appro)imation ass$mes that the n$,lei are stationar-, an.
ele,tron motion ,an be treate. separatel-. /i)e. bon. .istan,es an. bon. angles are ass$me.,
an. a Hamiltonian operator is "ritten %or ele,troni, motion onl- 0Mortimer, p.142.
2. 3sing the &orn'(ppenheimer appro)imation, "rite the Hamiltonian %or the H2
mole,$le 02 ele,trons2.
( )

+ + =
12 2 1 2 1 0
2
2
2
2
1
2
1 1 1 1 1 1
4 2
4
r r r r r R
e
m
H
B B A A AB

5
!&
5
12
5!2
5!1
5&2
5&1
! &
e
1
e
2
"here r!1 is the .istan,e bet"een n$,le$s ! an. ele,tron 16 r!2 is the .istan,e bet"een n$,le$s !
an. ele,tron 26 r&1 is the .istan,e bet"een n$,le$s & an. ele,tron 16 r&2 is the .istan,e bet"een
n$,le$s & an. ele,tron 26 r12 is the .istan,e bet"een ele,tron 1 an. ele,tron 26 an. 5!& is the
.istan,e bet"een n$,le$s ! an. n$,le$s & 0an. remains ,onstant b- the &orn'(ppenheimer
appro)imation2.
Variation Method; LCAO-MO
3. 7etermine the energ- %or
+
2
H in terms o% Haa, Hab, an. S $sing the 8ariation metho..
+he se,$lar .eterminant %or this s-stem is
0 =


bb bb ba ba
ab ab aa aa
ES H ES H
ES H ES H
9n this ,ase,
1 , , , = = = = = =
bb aa ba ab ba ab bb aa
S S S S S H H H H
, gi8ing
0 =


E H ES H
ES H E H
aa ab
ab aa
( ) ( )
( ) ( ) [ ] ( ) ( ) [ ]
( ) ( )
( )
S
H H
E
H H S E
H H S E E
S E H E H
ES H E H ES H E H
ES H E H
ab aa
ab aa
ab aa
ab aa
ab aa ab aa
ab aa
+
+
=
+ = +
+ = +
= +
= +
=
1
1
0
0
0
1
1
1 1
1 1
2 2
or
1
CHEM 342. Spring 2002. Problem Set #5. Mortimer Chapters 17, 1. !ns"ers.
( ) ( )
( )
S
H H
E
H H S E
H H S E E
S E H E H
ab aa
ab aa
ab aa
ab aa

=
=
=
=
1
1
0
2
2
2 2
2 2
Normalization; Hybrid Orbitals
4. Sho" that the sp
2
h-bri. orbital
( )
3
2
2
p s
sp
+
=
is normali:e. i% the s an. p orbitals
are also normali:e..
( ) ( ) ( ) 1 0 2 1
3
1
2 2 2
3
1
2
3
1
2 2
2
;
= + + = + + = + =

d sp p s d p s d
<ote= #e $se.

= 1
2
d s
6

= 1
2
d p
6 an.

= 0 spd
%or normali:e., orthogonal s
an. p orbitals.
Electronic Coni!"ration or Atoms # Molec"les; $a"li Excl"sion $rinciple
5. #hat are the ele,tron ,on%ig$rations %or H

, >i
?
, (
2
, /

, <a
?
, an. Mg
2?
*
( )
( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
1 2 2 2
1 2 2
1 2 2
1 2 2 2
2
2
2 2 1 =
2 2 1 =
2 2 1 =
2 2 1 =
1 =
1 =
p s s Mg
p s s Na
p s s F
p s s O
s Li
s H
+
+

1. #hi,h o% the %ollo"ing transitions are allo"e. in the normal ele,troni, emission
spe,tr$m o% an atom
0a2 2s to 1s
0b2 2p to 1s
0,2 3. to 2p
/or a single'ele,tron transition, 1 = l an. n @ an- integer.
0a2 not allo"e., 0 = l
0b2 allo"e., 1 = l
0,2 allo"e., 1 = l
7. #rite the ele,troni, ,on%ig$rations %or <2, <2
?
, <2

.
+he ,on%ig$rations are
( ) ( ) ( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) ( ) ( ) ( )
1
; 2 4
2
; 2
2
; 2
2
1 4
2
; 2
2
; 2
2
2 4
2
; 2
2
; 2
2
2 2 2 2 2 1 1 =
2 2 2 2 1 1 =
2 2 2 2 1 1 =
p p p s s s s N
p p s s s s N
p p s s s s N
g g u u g u g
g u u g u g
g u u g u g

+
%erm &ymbols or 'iatomics; Electronic %ransitions
2
CHEM 342. Spring 2002. Problem Set #5. Mortimer Chapters 17, 1. !ns"ers.
. 7etermine the ,omplete term s-mbol %or ea,h o% the %ollo"ing ele,troni,
,on%ig$rations
0a2 ( )
1
g

0b2 ( )
1
u

0,2 ( )
2
u

0.2 ( )
1
u

0e2 ( )
3
u

0a2 ( )
1
g
, the single $npaire. ele,tron gi8es a .o$blet state be,a$se S @ 1A2 so that
2 1
2
1
2 1 2 = +

= + S
. +he s-mbol is
+

g
2
0b2 ( )
1
u
, the term s-mbol is
+

u
2
0,2 ( )
2
u
, the ele,trons m$st be paire.. +here%ore, S @ 0 an. the state is a singlet. +he
pro.$,t o% t"o $ngera.e %$n,tions is gera.e. +he term s-mbol is
+

g
1
0.2 ( )
1
u
, the ele,tron ,o$l. be in either the ( ) 1 + =
+
or the ( ) 1 =

state.
+here%ore, there is a .egenerate pair o% states "ith 1 = an. the term s-mbol is
u

2
.
0e2 ( )
3
u
, there are t"o possible ,on%ig$rations=
( ) ( )
1 2
+
%or "hi,h 1 1 1 1 + = + = an.
( ) ( )
2 1
+
%or "hi,h 1 1 1 1 = = . +here%ore 1 = an. the state is . !lso,
the %$n,tion is $ngera.e be,a$se it is a pro.$,t o% three $ngera.e %$n,tions. +he term s-mbol is
there%ore
u

2
.
B. #rite the ele,troni, ,on%ig$ration %or >i2, an. pre.i,t the term s-mbol %or the gro$n.
le8el.
+he ele,troni, ,on%ig$ration is ( ) ( ) ( )
2
2
; 2
2 1 1 s s s
g u g
. /or this ,on%ig$ration, 0 =
L
M .
Sin,e L
M =
, "e Cno" that 0 = an. S @ 0, "hi,h res$lts in the s-mbol

1
. &e,a$se the
"a8e %$n,tion %or a

mole,$lar orbital .oes not ,hange sign $pon re%le,tion a,ross the xz
plane, the ? s$pers,ript is $se.. +he parit- ,an be %o$n. b- m$ltipl-ing the parities o% the
orbitals being $se., a,,or.ing to the la"s o% o.. 0u2 an. e8en 0g2 m$ltipli,ation=
u g u g u u g g g = = = 6 6
.
+here%ore, ( ) ( ) g u g =
2 4
, an. the ,omplete term s-mbol is
+

g
1
.
10. #hi,h o% the %ollo"ing ele,troni, transitions are allo"e.*
0a2
+ +

g u
1 1
0b2


g u
3 1
0,2
u g

+ 1 1
3
CHEM 342. Spring 2002. Problem Set #5. Mortimer Chapters 17, 1. !ns"ers.
+he sele,tion r$les %or ele,troni, transitions in .iatomi, mole,$les are
allo"e. not onl-6 an.
0
1 , 0
+ + +

=
=
u g
S
0a2
6 6 0 6 0 + + = = u g S
+he transition is allo"e..
0b2 +he transition is %orbi..en be,a$se 1 = S .
0,2

u g S = = 6 0 6 1
+he transition is allo"e..
11. +he gro$n.'le8el term %or a heteron$,lear .iatomi, mole,$le is

3
. #rite the term
s-mbols o% the ele,troni, transitions allo"e. %or this mole,$le.
!,,or.ing to the transition r$les 0see the pre8io$s problem2, the transition m$st be

6 the s$pers,ript m$st be 36 an. 0 = or 1 = . +he allo"e. transitions are


3 3
an.
3 3
. <ote that the notations g an. u are not $se. %or heteron$,lear .iatomi,
mole,$les.
4