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iu
Euition
Intiouuction to the Chemical Applications of uioup Theoiy
Page 2
Acknowleugments anu Web Resouices
These lectuie notes have been ueiiveu fiom seveial souices incluuing uioup Theoiy anu
Chemistiy by Baviu N. Bishop (ISBN1S: 978u48667SSS4) anu Chemical Applications
of uioup Theoiy by F. Albeit Cotton (ISBN1u: u47117S7u6).
Pictuies of moleculai oibitals weie calculateu using Fiiefly. The oibitals weie conveiteu to
cube foimat with Noluen anu ienueieu with PyNol.
Foi help with symmetiy opeiations anu symmetiy elements see:
http:www.molwave.comsoftwaieSumolsymSumolsym.htm
Animations of moleculai vibiations can be seen heie:
http:www.molwave.comsoftwaieSunoimalmouesSunoimalmoues.htm
Intiouuction to the Chemical Applications of uioup Theoiy
Page S
Table of Contents
Intiouuction ..................................................................................................................................... 6
Symmetiy Elements anu Symmetiy 0peiations .............................................................. 6
Iuentity (E) ....................................................................................................................................... 7
Rotation (C) ..................................................................................................................................... 7
Reflection () .................................................................................................................................. 8
Inveision (i) ..................................................................................................................................... 8
Impiopei Rotation (S)................................................................................................................. 9
Immeuiate Applications of Symmetiy ............................................................................... 1u
Symmetiy 0peiations............................................................................................................... 11
Algebia of 0peiatois ................................................................................................................. 12
Special case of lineai opeiatois ............................................................................................ 12
Algebia of lineai opeiatois .................................................................................................... 1S
Sum Law ......................................................................................................................................... 1S
Piouuct Law .................................................................................................................................. 1S
Associative Law ........................................................................................................................... 1S
Bistiibutive Law ......................................................................................................................... 1S
Algebia of Symmetiy 0peiatois .......................................................................................... 14
Associative Law: .................................................................................................................. 14
Bistiibutive Law: ................................................................................................................ 14
Befinition of a uioup ................................................................................................................. 16
Summaiy ........................................................................................................................................ 16
Example uioups .......................................................................................................................... 17
uioup Nultiplication Tables .................................................................................................. 18
Reaiiangement Theoiem: ...................................................................................................... 18
Classes ............................................................................................................................................. 2u
Similaiity Tiansfoims .............................................................................................................. 2u
Intiouuction to the Chemical Applications of uioup Theoiy
Page 4
Point uioups ................................................................................................................................. 22
Classification of Point uioups ............................................................................................... 2S
Systematic Nethou to Assign Point uioups .................................................................... 24
Classes in Symmetiy Point uioups ..................................................................................... 26
Piopeities of Natiices .............................................................................................................. 28
Natiix math basics ..................................................................................................................... 28
Auuition anu Subtiaction ................................................................................................ 28
Natiix multiplication ........................................................................................................ 29
Natiix Bivision .................................................................................................................... 29
Special Natiices ................................................................................................................... Su
Natiix Repiesentations of Symmetiy 0peiations........................................................ S1
Iuentity .................................................................................................................................... S1
Reflection ............................................................................................................................... S1
Inveision................................................................................................................................. S1
Rotation .................................................................................................................................. S2
Impiopei Rotations ........................................................................................................... SS
vectois anu Scalai Piouucts .................................................................................................. SS
Repiesentations of uioups ..................................................................................................... S6
The uieat 0ithogonality Theoiem ...................................................................................... S8
Iiieuucible Repiesentations .................................................................................................. S9
The Reuuction Foimula ........................................................................................................... 44
Chaiactei Tables ......................................................................................................................... 4S
Region I Nulliken Symbols foi Iiieuucible Repiesentations ............................... 4S
Region II Chaiacteis .............................................................................................................. 46
Region III Tianslations anu Rotations ........................................................................... 46
Region Iv Binaiy Piouucts ................................................................................................... 47
Wiiting Chemically Neaningful Repiesentations ......................................................... 47
Intiouuction to the Chemical Applications of uioup Theoiy
Page S
vibiations ...................................................................................................................................... 48
Selection Rules foi vibiations ............................................................................................... Su
Selection Rules foi Raman Spectioscopy ......................................................................... S1
Noimal Cooiuinate Analysis .......................................................................................... S2
IR anu Raman Spectia of CB
4
anu CB
S
F ............................................................................ 6u
Piojection 0peiatoi ................................................................................................................... 6S
Bonuing Theoiies ....................................................................................................................... 68
Lewis Bonuing Theoiy ............................................................................................................. 68
vSEPR valence Shell Election Paii Repulsion Theoiy ............................................ 68
valance Bonu Theoiy ................................................................................................................ 69
Bybiiu 0ibital Theoiy .............................................................................................................. 7u
Noleculai 0ibital Theoiy ........................................................................................................ 71
Quantum mechanical uesciiption of oibitals .......................................................... 7S
uioup Theoiy anu Quantum Nechanics ........................................................................... 74
LCA0 Appioximation ................................................................................................................ 7S
election Appioximation ...................................................................................................... 7S
Bckel 0ibital Nethou ......................................................................................................... 76
Bckel 0ibitals foi Nitiite ...................................................................................................... 77
Bckel N0s foi Cyclobutauiene .......................................................................................... 84
Bckel N0s foi Boion Tiifluoiiue ..................................................................................... 9u
0ne final exeicise .................................................................................................................... 9S
Intiouuction to the Chemical Applications of uioup Theoiy
Page 6
Introduction
Symmetiy: Relationship between paits of an object with iespect to size, shape
anu position.
Easy to iecognize symmetiy in natuie: Floweis, leaves, animals etc.
uioup Theoiy uevelopeu in the late 17uus. Eaily 18uus Evaiiste ualois
(181118S2) inventeu much of the funuamentals of gioup theoiy. This
coinciueu with uevelopments in matiix mathematics.
Chemists use a subset of gioup theoiy calleu iepiesentation theoiy.
uioup chaiacteis weie piimaiily the woik of ueoige Fiobenious (18491917)
Eaily chemical applications to quantum mechanics came fiom the woik of
Beimann Weyl (188S19SS) anu Eugene Wignei (19u2199S)
Symmetry Elements and Symmetry Operations
A symmetiy element is a geometiic entity (point, line oi plane)
A symmetiy opeiatoi peifoims anu action on a thiee uimensional object
Intiouuction to the Chemical Applications of uioup Theoiy
Page 7
Symmetiy opeiatois aie similai to othei mathematical opeiatois ( , , + ,
log, cos, etc)
We will be use only five types of opeiatois in this subject
0peiatoi Symbol
Iuentity E
Rotation C
Niiioi plane
Inveision i
Impiopei iotation S
All symmetiy opeiatois leave the shape (molecule) in an equivalent position,
i.e. it is inuistinguishable befoie anu aftei the opeiatoi has peifoimeu its
action.
Identity (E)
This opeiatoi uoes nothing anu is iequiieu foi completeness. Equivalent to
multiplying by 1 oi auuing u in algebia.
Rotation (C)
Rotate clockwise aiounu an axis by 2n if the iotation biings the shape
(molecule) into an equivalent position.
The symmetiy element is calleu the axis of symmetiy. Foi a 2\n iotation
theie is an nfolu axis of symmetiy. This is uenoteu as C
n
.
Nany molecules have moie than one symmetiy axis. The axis with the laigest
n is calleu the piincipal axis.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 8
Consiuei a squaie planai molecule like PtCl
4.
C
4
C
4
2
C
4
3
C
4
4
possible iotations. C
4
2
C
2
anu C
4
4
E
We classify this as E, 2C
4
, C
2
. Theie aie also two othei C
2
axes (along the
bonus anu between the bonus)
Reflection ()
The shape (molecule) is ieflecteu thiough a plane. (spiegel is ueiman foi
miiioi)
If a plane is to the piincipal iotation axis then it is calleu
h
(hoiizontal). If it
is along the piincipal axis then it is calleu
v
(veitical). Theie may be moie
than one
v
. If the plane bisects an angle between S atoms then it is calleu
u
(uiheuial).
The ieflection plane is the symmetiy element.
Inversion (i)
All points in the shape (molecule) aie ieflecteu though a single point. The
point is the symmetiy element foi inveision. This tuins the molecule insiue
out in a sense. The symmetiy element is the point thiough which the shape is
inveiteu.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 9
Improper Rotation (S)
Rotation by 2n followeu by ieflection, to the iotation axis. Since
peifoiming two times is the same as uoing nothing (E), S can only be
peifoimeu an ouu numbei of time.
S
n
k
= o
h
C
n
k
if k is ouu
S
n
k
= C
n
k
if k is even
k must be an ouu value
e.g. S
3
2
= C
3
2
anu S
3
5
= o
h
C
3
5
Auuitionally
S
1
= o
h
S
n
n
= o
h
if n is ouu
S
n
n
= E if n is even
The symmetiy element foi S is the iotation axis.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 1u
Immediate Applications of Symmetry
Bipole Noments
If a molecule has a uipole moment then the uipole must lie along the
symmetiy elements (lines, planes).
If a molecule has axis of iotation, then no uipole exists.
If theie is a , then the uipole must lie within the plane. If theie aie
multiple the uipole must lie at the inteisection of the planes.
If a molecule has an inveision centei (i) then no uipole exists.
Examples with B
2
0, NB
S
, PtCl
4
.
0ptical Activity
In geneial, if a molecule has an impiopei iotation (S
n
), then it is optically
inactive. This is because, a molecule with an S
n
is always supeiimposable on
its miiioi image.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 11
Symmetry Operations
Iuentifying all symmetiy elements anu opeiations in molecules.
Cyclopiopane B
Sh
E, 2C
S
, SC
2
,
h,
2S
S
, S
v
Theie is an S
3
1
anu an S
3
5
(also calleu S
3
-1
)
Ethane (staggeieu) B
Su
E, 2C
S
, SC
2
, i, 2S
6
, S
u
1,S,Stiihyuioxybenzene (planai) C
Sh
E, 2C
S
,
h
2S
S
Theie is an S
3
1
anu an S
3
5
(also calleu S
3
-1
)
Intiouuction to the Chemical Applications of uioup Theoiy
Page 12
Algebra of Operators
An opeiatoi is a symbol foi the opeiation (iotation, ieflection, etc)
e.g. C
S
is the opeiatoi foi the opeiation of clockwise iotation by 2S
0peiatois can opeiate on functions f(x) to geneiate new functions
e.g. 0 multiply by S
f(x) = 2+Sx
2
Then 0f(x) = 6+9x
2
0 can be uefineu any way we like, uux , ( )
2
, etc
Special case of linear operators
Lineai opeiatois have the following piopeity
0(f
1
+ f
2
) = 0f
1
+ 0f
2
Anu 0(kf
1
) = k0f
1
wheie k is a constant
Biffeientiation cleaily is a lineai opeiatoi
J
Jx
(x
2
+ x) = 2x + 1 oi
J
Jx
x
2
+
J
Jx
x = 2x + 1
anu
J
Jx
Sx
2
= S
J
Jx
x
2
= 6x
Intiouuction to the Chemical Applications of uioup Theoiy
Page 1S
Algebra of linear operators
1. Sum Law
2. Piouuct Law
S. Associative Law
4. Bistiibutive Law
Sum Law
(0
1
+ 0
2
)(x) = 0
1
(x) + 0
2
(x)
Product Law
0
1
0
2
(x) = 0
1
(0
2
(x))
0
2
opeiates fiist to piouuce a new function, then 0
1
opeiates to piouuce
anothei new function.
Note: the oiuei of opeiations is impoitant heie. 0
1
0
2
may not be the same as
0
2
0
1
, i.e. opeiatois uo not necessaiily commute with each othei.
Associative Law
0
1
(0
2
0
3
) = (0
1
0
2
)0
3
2
nu
1
st
2
nu
1
st
Distributive Law
0
1
(0
2
+ 0
3
) = 0
1
0
2
+ 0
1
0
3
anu
(0
2
+ 0
3
)0
1
= 0
2
0
1
+ 0
3
0
1
Bo symmetiy opeiatois obey these laws. (they uo)
Intiouuction to the Chemical Applications of uioup Theoiy
Page 14
consiuei acetone E, C
2
,
v1
,
v2
Sum Law: theie is no piocess to auu symmetiy opeiatois
Algebra of Symmetry Operators
Piouuct Law:
We uefine the piouuct of symmetiy opeiatois as: uo one opeiation followeu
by anothei:
e.g. PQf means apply Q to f anu then apply P to the iesult wheie P anu Q aie
some symmetiy opeiation. 0i, alteinatively PQ = R wheie R is also a
symmetiy opeiation.
(C
2
v1
)f = C
2
(
v1
)f
C
2
v1
v2
anu C
2
(
v1
)f iesults in the same configuiation as
v2
f
Associative Law:
C
2
(
v1
v2
)f = (C
2
v1
)
v2
f
v1
v2
C
2
C
2
v1
v2
C
2
C
2
E
v2
v2
E
ueneiically (PQ)R = P(QR)
Distributive Law:
Theie is no piocess to auu symmetiy opeiatois
Intiouuction to the Chemical Applications of uioup Theoiy
Page 1S
Consiuei the ammonia molecule (C
Sv
)
E, 2C
S
, S
v
Note heie that C
3
1
C
3
2
= E
If two opeiatois combine to give the iuentity, we say that they aie inveise to
each othei.
C
3
2
= C
3
-1
onJ C
3
C
3
-1
= E = C
3
C
3
2
It is also tiue that C
3
C
3
-1
= C
3
-1
C
3
= E oi geneiically PQ = QP = E
i.e. symmetiy opeiatois that aie inveise to one anothei commute.
h
= E
ii =E
miiioi planes aie always inveise to themselves, likewise inveision is always
inveise to itself.
ueneiically we wiite (PQ)
1
= P
1
Q
1
Intiouuction to the Chemical Applications of uioup Theoiy
Page 16
Definition of a Group
Theie aie foui uefining iules foi gioups.
1. The combination of any two elements as well as the squaie of each
element must be in the gioup.
Combining iule can be uefineu as anything (multiplication, uiffeientiation, one
followeu by anothei, etc)
PQ = R ; R must be in the gioup
The commutative law may not holu AB = BA
2. 0ne element must commute with all othei elements anu leave them
unchangeu. That is, an iuentity element must be piesent.
ER = RE =R ; E must be in the gioup
S. The associative law must holu.
P(QR) = (PQ)R ; foi all elements
4. Eveiy element must have an inveise which is also in the gioup.
RR
1
= R
1
R = E ; R
1
must be in the gioup
Summary
Befinition of a gioup
PQ = R
R must be in the gioup
ER = RE =R
E must be in the gioup
P(QR) = (PQ)R
foi all elements
RR
1
= R
1
R = E
R
1
must be in the gioup
Intiouuction to the Chemical Applications of uioup Theoiy
Page 17
Example Groups
With a combining iule of auuition, all integeis foim a gioup.
The iuentity element is u, anu the inveise of each element is the negative
value.
This is an example of an infinite gioup.
============================================
With a combining iule of multiplication, we can foim a finite gioup with the
following set {i, i, 1, 1]
The iuentity element is 1 in this case.
============================================
A set of matiices can also foim a finite gioup with the combining iule of
matiix multiplication.
_
1 u u u
u 1 u u
u u 1 u
u u u 1
_ _
u 1 u u
1 u u u
u u u 1
u u 1 u
_ _
u u u 1
u u 1 u
u 1 u u
1 u u u
_ _
u u 1 u
u u u 1
1 u u u
u 1 u u
_
The iuentity matiix is _
1 u u u
u 1 u u
u u 1 u
u u u 1
_
e.g.
_
u 1 u u
1 u u u
u u u 1
u u 1 u
_ _
u u u 1
u u 1 u
u 1 u u
1 u u u
_ = _
u u 1 u
u u u 1
1 u u u
u 1 u u
_
o
k
b
k]
= (AB)
]
n
k
a
ik
=element in the i
th
iow anu k
th
column
Intiouuction to the Chemical Applications of uioup Theoiy
Page 18
Lastly, the set of symmetiy opeiatois (not symmetiy elements) piesent foi a
given moleculai shape foims a gioup with the combining iule of one followeu
by anothei.
These types of gioups aie calleu point gioups.
Group Multiplication Tables
The numbei of elements (symmetiy opeiatois) in the gioup is calleu the
oiuei of the gioup (h)
Rearrangement Theorem:
In a gioup multiplication table, each iow anu column lists each element in the
gioup once anu only once. No two iows oi two columns may be iuentical.
Consiuei a gioup of oiuei S
u
S
E A B
E E A B
A A . .
B B . .
Theie aie two options foi filling out the table AA = B oi AA = E
If AA = E then the table becomes
u
S
E A B
E E A B
A A E B
B B A E
This violates the ieaiiangement theoiem as the last two columns have
elements that appeai moie than once.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 19
The only solution foi gioup u
S
is
u
S
E A B
E E A B
A A B E
B B E A
Note: The gioup u
S
is a membei of a set of gioups calleu cyclic gioups. Cyclic
gioups have the piopeity of being Abelian, that is all elements commute with
each othei.
A cyclic gioup is one which eveiy element can be geneiateu by a single
element anu its poweis. In this case A = A anu AA = A
2
= B anu AAA = A
S
=
E.
Theie aie two possible gioups of oiuei 4
u
4
E A B C
E E A B C
A A B C E
B B C E A
C C E A B
u
4
E A B C
E E A B C
A A E C B
B B C E A
C C B A E
In the seconu case of u
4
theie is a subgioup of oiuei 2 piesent.
u
2
E A
E E A
A A E
The oiuei of a subgioup (g) must be a uivisoi of the oiuei of the main gioup
(h), that is hg = k, wheie k is an integei.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 2u
Classes
uioups can fuithei be uiviueu into smallei sets calleu classes.
Similarity Transforms
If A, B anu X aie in a gioup anu X
1
AX = B we say that B is similaiity
tiansfoim of A by X. We also can say that A anu B aie conjugate of each othei.
Conjugate elements have the following piopeities
1) All elements aie conjugate with themselves
A = X
1
AX foi some X
2) If A is conjugate to B, then B is conjugate to A
A = X
1
BX anu B = Y
1
AY with X, Y in the gioup
S) If A is conjugate to B anu C then B anu C aie also conjugates of each
othei.
The complete set of elements (opeiations) that aie conjugate to each othei is
calleu a class.
Finu the classes in u
6
u
6
E A B C B F
E E A B C B F
A A E B F B C
B B F E B C A
C C B F E A B
B B C A B F E
F F B C A E B
E is in a class by itself of oiuei 1
A
1
EA = E etc..
Intiouuction to the Chemical Applications of uioup Theoiy
Page 21
0thei classes in u
6
E
1
AE = A
A
1
AA = A
B
1
AB = C
C
1
AC = B
B
1
AB = B
F
1
AF = C
We see heie that the elements A,B anu C aie all conjugate to each othei anu
foim a class of oiuei S.
E
1
BE = B
A
1
BA = F
B
1
BB = F
C
1
BC = F
B
1
BB = B
F
1
BF = B
We see heie that the elements B anu F aie conjugate to each othei anu foim a
class of oiuei 2.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 22
Point Groups
Consiuei all of the symmetiy opeiations in NB
S
E
v
v
v
C
S
C
3
2
NB
S
E
v
v
v
C
S
C
3
2
E E
v
v
v
C
S
C
3
2
v
v
E C
S
C
3
2
v
v
v
v
C
3
2
E C
S
v
v
v
v
C
S
C
3
2
E
v
v
C
S
C
S
v
v
v
C
3
2
E
C
3
2
C
3
2
v
v
v
E C
S
Note that all of the iules of a gioup aie obeyeu foi the set of alloweu
symmetiy opeiations in NB
S
.
u
6
E A B C B F
E E A B C B F
A A E B F B C
B B F E B C A
C C B F E A B
B B C A B F E
F F B C A E B
Compaie the multiplication table of NB
S
to that of u
6
.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 2S
Theie is a 1:1 coiiesponuence between the elements in each gioup
E E
v
A
v
B
v
C
C
S
B
C
3
2
F
uioups that have a 1:1 coiiesponuence aie saiu to be isomoiphic to each
othei.
If theie is a moie than 1:1 coiiesponuence between two gioups, they aie saiu
to be homomoiphic to each othei. All gioups aie homomoiphic with the
gioup E. i.e. A E , B E, C E etc
Classification of Point Groups
Schoenflies Notation
uioup
Name
Essential Symmetiy
Elements*
C
s
one
C
i
one i
C
n
one C
n
B
n
one C
n
plus nC
2
to C
n
C
nv
one C
n
plus n
v
C
nh
one C
n
plus
h
B
nh
those of B
n
plus
h
B
nu
those of B
n
plus
u
S
n
(even n) one S
n
T
u
tetiaheuion
Special uioups
0
h
octaheuion
I
h
icosaheuions
B
h
spheie
Intiouuction to the Chemical Applications of uioup Theoiy
Page 24
Systematic Method to Assign Point Groups
Intiouuction to the Chemical Applications of uioup Theoiy
Page 2S
Assign the point gioups to the following molecules
i only C
i
C
n
C
S
C
Sh
C
Sv
Intiouuction to the Chemical Applications of uioup Theoiy
Page 26
Classes in Symmetry Point Groups
You can test all possible similaiity tiansfoims to finu the conjugate elements.
X
1
AX = B , howevei this is teuious anu with symmetiy elements it is much
easiei to soit classes.
Two opeiations belong to the same class if one may be ieplaceu by anothei in
a new cooiuinate system which is accessible by an alloweu symmetiy
opeiation in the gioup.
Consiuei the following foi a B
4h
gioup
C
4
|x,y] |y, x] anu C
4
3
|x,y] |y,x]
Reflect the cooiuinate system by
u
C
4
i
|x,y] |y, x] anu C
4
3i
|x,y] |y,x]
By changing the cooiuinate system we have simply ieplace the ioles that C
4
anu C
4
3
play. That is C
4
i
C
4
3
anu C
4
3i
C
4
Intiouuction to the Chemical Applications of uioup Theoiy
Page 27
Noie geneially we can state the following
1. E, i anu
h
aie always in a class by themselves.
2. C
n
k
anu C
n
-k
aie in the same class foi each value of k as long as theie is a
plane of symmetiy along the C
n
k
axis oi a C
2
to C
n
k
. If not then
C
n
k
anu C
n
-k
aie in classes by themselves. Likewise foi S
n
k
anu S
n
-k
.
S. anu aie in the same class if theie is an opeiation which moves one
plane into the othei. Likewise foi C
n
k
anu C
n
k
that aie along uiffeient
axes.
Consiuei the elements of B
4h
(squaie plane)
Theie aie 1u classes in this gioup with oiuei 14
E
C
4
anu C
4
-1
i
v
anu
v
u
anu
u
C
2
(along z)
C
2
i
anu C
2
ii
(xy)
C
2
i
anu C
2
ii
(x,y)
S
4
anu S
4
-1
Intiouuction to the Chemical Applications of uioup Theoiy
Page 28
Properties of Matrices
Natiix: iectangulai aiiay of numbeis oi elements
A = _
o
11
o
12
o
13
o
21
o
22
o
23
o
31
o
32
o
33
_ a
ij
i
th
iow anu j
th
column
A vectoi is a one uimensional matiix
_
o
11
o
21
o
31
_ This coulu be a set of Caitesian cooiuinates (x,y,z)
Matrix math basics
Addition and Subtraction
Natiices must be the same size
C
ij
= A
ij
_ B
ij
auu oi subtiact the coiiesponuing elements in each matiix
Nultiplication by a scalai (k)
k|a
ij
] = |ka
ij
] eveiy element is multiplieu by the constant k
Intiouuction to the Chemical Applications of uioup Theoiy
Page 29
Matrix multiplication
AB = o
k
b
k]
= c
]
n
k
a
ik
=element in the i
th
iow anu k
th
column
_
o
11
o
12
o
21
o
22
o
31
o
32
_ _
b
11
b
12
b
13
b
21
b
22
b
23
_ = _
c
11
c
12
c
13
c
21
c
22
c
23
c
31
c
32
c
33
_
Wheie c
11
= (a
11
b
11
+ a
12
b
21
)
c
12
= (a
11
b
12
+ a
12
b
22
)
etc
matiix multiplication is not commutative (AB = BA)
Matrix Division
Bivision is uefineu as multiplying by the inveise of a matiix. 0nly squaie
matiices may have an inveise.
The inveise of a matiix is uefineu as
AA
1
=
ij
ij
Kioneckei uelta
ij
= 1 if i = j otheiwise
ij
= u
o
]
= _
1 u u
u 1 u
u u 1
_
Intiouuction to the Chemical Applications of uioup Theoiy
Page Su
Special Matrices
Block uiagonal matiix multiplication
l
l
l
l
l
l
1 u u u u u
1 2 u u u u
u u S u u u
u u u 1 S 2
u u u 1 2 2
u u u 4 u 1
1
1
1
1
1
1
l
l
l
l
l
l
4 1 u u u u
2 S u u u u
u u 1 u u u
u u u u 1 2
u u u S u 2
u u u 2 1 1
1
1
1
1
1
1
=
l
l
l
l
l
l
4 1 u u u u
8 7 u u u u
u u S u u u
u u u 1S S 1u
u u u 1u S 8
u u u 2 S 9
1
1
1
1
1
1
Each block is multiplieu inuepenuently
i.e.
j
1 u
1 2
[ j
4 1
2 S
[ = j
4 1
8 7
[
|S]|1] = |S]
_
1 S 2
1 2 2
4 u 1
_ _
u 1 2
S u 2
2 1 1
_ = _
1S S 1u
1u S 8
2 S 9
_
Squaie Natiices
_
A
= o
]] ]
This is the sum of the uiagonal elements of a matiix (tiace).
A
is calleu the chaiactei of matiix A
piopeities of
if C = AB anu B = BA then
C
=
B
conjugate matiices have iuentical
P = B
1
PB then
R
=
B
Theiefoie, opeiations that aie in the same class have the same chaiactei.
Intiouuction to the Chemical Applications of uioup Theoiy
Page S1
Matrix Representations of Symmetry Operations
We will now use matiices to iepiesent symmetiy opeiations.
Consiuei how an {x,y,z] vectoi is tiansfoimeu in space
Identity
E
_
1 u u
u 1 u
u u 1
_ _
x
y
z
_ = _
x
y
z
_
Reflection
xy
_
1 u u
u 1 u
u u -1
_ _
x
y
z
_ = _
x
y
-z
_
xz
_
1 u u
u -1 u
u u 1
_ _
x
y
z
_ = _
x
-y
z
_
Inversion
i
_
-1 u u
u -1 u
u u -1
_ _
x
y
z
_ = _
-x
-y
-z
_
Intiouuction to the Chemical Applications of uioup Theoiy
Page S2
Rotation
C
n
about the z axis
_
. . u
. . u
u u 1
_ _
x
y
z
_ = _
x
y
z
_ The z cooiuinate iemains unchangeu.
Consiuei a countei clockwise iotation by about the z axis
Fiom tiigonometiy we know that
x
2
= x
1
cos 0 - y
1
sin0 anu y
2
= x
1
sin0 + y
1
cos 0
Repiesenteu in matiix foim this gives:
j
cos 0 -sin0
sin0 cos 0
[ j
x
1
y
1
[ = j
x
2
x
2
[
Foi a clockwise iotation we finu
_
cos sin
-sin cos
_ j
x
1
y
1
[ = j
x
2
x
2
[ iecall cos = cos(-) onJ sin = -sin(-)
The tiansfoimation matiix foi a clockwise iotation by is:
_
cos sin u
-sin cos u
u u 1
_ _
x
y
z
_ = _
x
y
z
_
Intiouuction to the Chemical Applications of uioup Theoiy
Page SS
Improper Rotations
S
n
Because an impiopei iotation may be expiesseu as
xy
C
n
we can wiite the
following since matiices also follow the associative law.
_
1 u u
u 1 u
u u -1
_ _
cos sin u
-sin cos u
u u 1
_ _
x
y
z
_ = _
x
y
z
_
_
cos sin u
-sin cos u
u u -1
_ _
x
y
z
_ = _
x
y
z
_
The set of matiices that we have geneiateu that tiansfoim a set of {x,y,z]
oithogonal cooiuinates aie calleu oithogonal matiices. The inveise of these
matiices aie founu by exchanging iows into columns (taking the tianspose of
the matiix).
Consiuei a C
S
iotation about the zaxis.
l
l
l
l
-
1
2
3
2
u
-
3
2
-
1
2
u
u u 1
1
1
1
1
= C
3
exchanging iows into columns gives
l
l
l
l
-
1
2
-
3
2
u
3
2
-
1
2
u
u u 1
1
1
1
1
= (C
3
)
1
= C
3
2
Intiouuction to the Chemical Applications of uioup Theoiy
Page S4
Nultiplying these two matiices gives the iuentity matiix
l
l
l
l
-
1
2
3
2
u
-
3
2
-
1
2
u
u u 1
1
1
1
1
l
l
l
l
-
1
2
-
3
2
u
3
2
-
1
2
u
u u 1
1
1
1
1
= _
1 u u
u 1 u
u u 1
_
We alieauy know fiom symmetiy that C
3
C
3
2
= C
3
2
C
3
= E
Beie we see that C
3
anu C
3
2
aie inveise anu oithogonal to each othei.
In geneial we can wiite a set of homomoiphic matiices that foim a
iepiesentation of a given point gioup
Foi example, consiuei the watei molecule which belongs to the C
2v
gioup.
C
2v
contains E, C
2
,
xz
,
yz
The set of foui matiices below tiansfoim anu multiply exactly like the
symmetiy opeiations in C
2v
. That is, they aie homomoiphic to the symmetiy
opeiations.
_
1 u u
u 1 u
u u 1
_ , _
-1 u u
u -1 u
u u 1
_ , _
1 u u
u -1 u
u u 1
_ , _
-1 u u
u 1 u
u u 1
_
E C
2
xz
yz
Show that C
2
xz
=
yz
_
-1 u u
u -1 u
u u 1
_ _
1 u u
u -1 u
u u 1
_ = _
-1 u u
u 1 u
u u 1
_
The algebia of matiix multiplication has been substituteu foi the geometiy of
applying symmetiy opeiations.
Intiouuction to the Chemical Applications of uioup Theoiy
Page SS
Vectors and Scalar Products
Consiuei two vectois in 2B space
The scalai oi uot piouuct iesults in a scalai oi numbei
Befineu as the length of each vectoi times each othei times the cos of the
angle between them: AB = ABcos
If = 9u then AB = u
If = u then AB = AB
We can wiite the following:
= angle to the x axis foi A
= gieatei angle to the x axis foi B ( = + )
Piojections
A
x
= A cos
A
y
= A sin
B
x
= B cos
B
y
= B sin
Intiouuction to the Chemical Applications of uioup Theoiy
Page S6
0sing a tiig iuentity we can wiite
AB = AB(cos cos + sin sin )
Reaiiange to A cos B cos + A sin B sin
Substitute fiom above
AB = A
x
B
x
+ A
y
B
y
Noie geneially
A B = A
= u
n
=1
Representations of Groups
The following matiices foim a iepiesentation of the C
2v
point gioup
_
1 u u
u 1 u
u u 1
_ , _
-1 u u
u -1 u
u u 1
_ , _
1 u u
u -1 u
u u 1
_ , _
-1 u u
u 1 u
u u 1
_
E C
2
xz
yz
uioup Nultiplication Table foi C
2v
C
2v
E C
2
xz
yz
E E C
2
xz
yz
C
2
C
2
E
yz
xz
xz
xz
yz
E C
2
yz
yz
xz
C
2
E
Intiouuction to the Chemical Applications of uioup Theoiy
Page S7
Bow many othei iepiesentations exist foi the C
2v
point gioup.
A: As many as we can think up
The set of numbeis {1,1,1,1] tiansfoim like C
2v
etc
Bowevei, theie aie only a few iepiesentations that aie of funuamental
impoitance.
Consiuei the matiices E, A, B, C, anu we peifoim a similaiity tiansfoim with
Q
E = Q
1
EQ
A = Q
1
AQ
B = Q
1
BQ
Etc
Foi example A = Q
1
AQ
A = Q
1
AQ =
A
1
i
A
2
i
A
3
i
A
4
i
The similaiity tiansfoim of A by Q will block uiagonalize all of the matiices
All of the iesulting subsets foim iepiesentations of the gioup as well
e.g. F
1
i
, A
1
i
, B
1
i
ctc .
We say that E, A, B, C aie ieuucible matiices that foim a set of ieuucible
iepiesentations.
If Q uoes not exist which will block uiagonalize all of the matiix
iepiesentations then we have an iiieuucible iepiesentation.
Intiouuction to the Chemical Applications of uioup Theoiy
Page S8
The Great Orthogonality Theorem
The theoiem states
|
(R)
mn
]|
]
(R)
m
|
n
|]
R
=
b
l
]
o
]
o
mm
| o
nn
|
Wheie;
h = oiuei of the gioup (# of symmetiy opeiatois)
= i
th
iepiesentation
l
= uimension of
( e.g. S S , l
= S)
R = geneiic symbol foi an opeiatoi
|
(R)
mn
] = the element in the m
th
iow anu n
th
column of an opeiatoi R in
iepiesentation
|
]
(R)
m
|
n
| ]
(R)
mn
]|
]
(R)
m
|
n
| ]
R
= u if i = j
If vectois aie fiom the same iepiesentation but aie uiffeient sets of elements
then they aie oithogonal
|
(R)
mn
]|
(R)
m
|
n
|]
R
= u if m = m' oi n = n'
The squaie of the length of any vectoi is hl
i
|
(R)
mn
]|
(R)
mn
]
R
=
b
l
Irreducible Representations
Theie aie five impoitant iules conceining iiieuucible iepiesentations
1) The sum of the squaies of the uimensions of the iiieuucible
iepiesentations of a gioup is equal to the oiuei of the gioup
l
2
= b
2) The sum of the squaies of the chaiacteis in an iiieuucible
iepiesentation is equal to the oiuei of the gioup
|_
(R)]
2
= b
Intiouuction to the Chemical Applications of uioup Theoiy
Page 4u
S) vectois whose components aie the chaiacteis of two iiieuucible
iepiesentations aie oithogonal
|_
(R)]|_
]
(R)]
= u when i = j
4) In a given iepiesentation (ieuucible oi iiieuucible) the chaiacteis of all
matiices belonging to the same class aie iuentical
S) The numbei of iiieuucible iepiesentations of a gioup is equal to the
numbei of classes in the gioup.
Lets look at a simple gioup , C
2v
(E, C
2
,
v
,
v
)
Theie aie foui elements each in a sepaiate class. By iule S, theie must be 4
iiieuucible iepiesentations. By iule 1, the sum of the squaies of the
uimensions must be equal to h (4).
l
1
2
+ l
2
2
+ l
3
2
+ l
4
2
= 4
The only solution is l
1
= l
2
= l
3
= l
4
= 1
Theiefoie the C
2v
point gioup must have foui one uimensional iiieuucible
iepiesentations.
C
2v
E C
2
v
v
1
1 1 1 1
All othei iepiesentations must satisfy |_
(R)]
2
= 4
This can only woik foi
i
= _ 1. Anu foi each of the iemaining to be
oithogonal to
1
theie must be two +1 anu two 1.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 41
Theiefoie, the iemaining must be (E is always +1)
C
2v
E C
2
v
v
1
1 1 1 1
2
1 1 1 1
S
1 1 1 1
4
1 1 1 1
Take any two anu veiify that they aie oithogonal
2
= (11) + (11) + (11) +(11) = u
These aie the foui iiieuucible iepiesentation of the point gioup C
2v
Consiuei the C
Sv
gioup (E, 2C
S
, S
v
)
Theie aie thiee classes so theie must be thiee iiieuucible iepiesentations
l
1
2
+ l
2
2
+ l
3
2
= 6
The only values which woik aie l
1
= 1 , l
2
= 1 , l
3
= 2
That is, two one uimensional iepiesentations anu one two uimensional
iepiesentation.
So foi
1
we can choose
C
Sv
E 2C
S
S
v
1
1 1 1
Foi
2
we neeu to choose _ 1 to keep oithogonality
C
Sv
E 2C
S
S
v
1
1 1 1
2
1 1 1
1
2
= (11) + 2(11) + S(11) = u
Intiouuction to the Chemical Applications of uioup Theoiy
Page 42
C
Sv
E 2C
S
S
v
1
1 1 1
2
1 1 1
S
2
To finu
S
we must solve the following
|_
1
(R)]|_
3
(R)]
= (1)(2) + 2(1)|_
3
(C
3
)] + S(1)|_
3
(o
)] = u
|_
2
(R)]|_
3
(R)]
= (1)(2) + 2(1)|_
3
(C
3
)] + S(-1)|_
3
(o
)] = u
Solving this set of two lineai equation anu two unknowns gives
|_
3
(C
3
)] = -1 anu |_
3
(o
)] = u
Theiefoie the complete set of iiieuucible iepiesentations is
C
Sv
E 2C
S
S
v
1
1 1 1
2
1 1 1
S
2 1 u
We have ueiiveu the chaiactei tables foi C
2v
anu C
Sv
(check the book
appenuix)
C
2v
E C
2
v
v
C
Sv
E 2C
S
S
v
A
1
1 1 1 1 A
1
1 1 1
A
2
1 1 1 1 A
2
1 1 1
B
1
1 1 1 1 E 2 1 u
B
2
1 1 1 1
Intiouuction to the Chemical Applications of uioup Theoiy
Page 4S
We now know that theie is a similaiity tiansfoim that may block uiagonalize a
ieuucible iepiesentation. Buiing a similaiity tiansfoim the chaiactei of a
iepiesentation is left unchangeu.
_(R) = o
]
_
]
(R)
]
Wheie (R) is the chaiactei of the matiix foi opeiation R anu a
j
is the numbei
of times that the j
th
iiieuucible iepiesentation appeais along the uiagonal.
The goou news is that we uo not neeu to finu the matiix Q to peifoim the
similaiity tiansfoim anu block uiagonalize the matiix iepiesentations.
Because the chaiacteis aie left intact, we can woik with the chaiacteis alone.
We will multiply the above by
i
(R) anu sum ovei all opeiations.
_(R)
R
_
(R) = o
]
_
]
(R)
]
_
(R)
R
= o
]
_
]
(R)
R
_
(R)
]
anu
_
(R)
R
_
]
(R) = bo
]
Recall that
_
2
(R)
R
= b
Foi each sum ovei j we have
o
]
_
]
(R)
R
_
(R) = o
]
_
]
(R)
R
_
(R) = o
]
bo
]
The chaiacteis foi
i
anu
j
foim oithogonal vectois we can only have non
zeio values when i = j
Intiouuction to the Chemical Applications of uioup Theoiy
Page 44
The Reduction Formula
The above leaus to the impoitant iesult calleu The Reuuction Foimula
o
=
1
b
_(R)
R
_
(R)
Wheie a
i
is the numbei of times the i
th
iiieuucible iepiesentation appeais in
the ieuucible iepiesentation.
C
Sv
E 2C
S
S
v
1
1 1 1
2
1 1 1
S
2 1 u
a
S 2 1
b
7 1 S
Apply the ieuuction foimula to
a
anu
b
Foi
a
o
1
=
1
6
|(1)(1)(S) + (2)(1)(2) + (S)(1)(-1) = 1
o
2
=
1
6
|(1)(1)(S) + (2)(1)(2) + (S)(-1)(-1) = 2
o
3
=
1
6
|(1)(2)(S) + (2)(-1)(2) + (S)(u)(-1) = 1
Foi
b
o
1
=
1
6
|(1)(1)(7) + (2)(1)(1) + (S)(1)(-S) = u
o
2
=
1
6
|(1)(1)(7) + (2)(1)(1) + (S)(-1)(-S) = S
o
3
=
1
6
|(1)(2)(7) + (2)(-1)(1) + (S)(u)(-S) = 2
Intiouuction to the Chemical Applications of uioup Theoiy
Page 4S
Sum the columns
Foi
a
C
Sv
E 2C
S
S
v
1
1 1 1
2
1 1 1
2
1 1 1
S
2 1 u
a
S 2 1
Foi
b
C
Sv
E 2C
S
S
v
2
1 1 1
2
1 1 1
2
1 1 1
S
2 1 u
S
2 1 u
b
7 1 S
Character Tables
Foi C
Sv
we finu the following chaiactei table with foui iegions, IIv.
C
Sv
E 2 C
S
S
v
A
1
1 1 1 z x
2
+y
2
, z
2
A
2
1 1 1 R
z
E 2 1 u (x,y)(R
x
,R
y
) (x
2
y
2
, xy)(xz,yz)
I II III Iv
Region I Mulliken Symbols for Irreducible Representations
1) All 11 iepiesentations aie A oi B, 22 aie E anu SS aie T
Intiouuction to the Chemical Applications of uioup Theoiy
Page 46
2) 11 which aie symmetiic with iespect to iotation by 2n about the
piinciple C
n
axis aie A (i.e. the chaiactei is +1 unuei C
n
). Those that
aie antisymmetiic aie labeleu B (the chaiactei is 1 unuei C
n
).
S) Subsciipts 1 oi 2 aie auueu to A anu B to uesignate those that aie
symmetiic (1) oi antisymmetiic (2) to a C
2
to C
n
oi if no C
2
is piesent
then to a
v
.
4) anu aie attacheu to those that aie symmetiic () oi antisymmetiic
()ielative to a
h
.
S) In gioups with an inveision centei (i), subsciipt g (ueiman foi geiaue
oi even) is auueu foi those that aie symmetiic with iespect to i oi a
subsciipt u (ueiman foi ungeiaue oi uneven) is auueu foi those anti
symmetiic with iespect to i.
6) Labels foi E anu T iepiesentations aie moie complicateu but follow the
same geneial iules.
Region II Characters
This iegion list the chaiacteis of the iiieuucible iepiesentations foi all
symmetiy opeiations in each gioup.
Region III Translations and Rotations
The iegion assigns tianslations in x,y anu z anu iotations R
x
, R
y
, R
z
to
iiieuucible iepiesentations. E.g., in the gioup above (x,y) is listeu in the same
iow as the E iiieuucible iepiesentation. This means that if one foimeu a
matiix iepiesentation baseu on x anu y cooiuinates, it woulu tiansfoim (that
is have the same chaiacteis as) iuentically as E.
Recall that pieviously we lookeu at a C
S
tiansfoimation matiix foi a set of
Caitesian cooiuinates
l
l
l
l
-
1
2
3
2
u
-
3
2
-
1
2
u
u u 1
1
1
1
1
_
x
y
z
_ = _
x
y
z
_ = C
3
Notice that this matiix is block uiagonalizeu. If we bieak this into blocks we
aie left with
Intiouuction to the Chemical Applications of uioup Theoiy
Page 47
_
-
1
2
3
2
-
3
2
-
1
2
_ j
x
y
[ = _
x
i
y
i
_ = C
3
anu |1]|z] = |z
i
] = C
3
Compaie the chaiacteis of these matiices to the chaiacteis unuei C
S
in the
table above. Notice that foi (x,y) = 1 anu foi (z) = 1. If you compaieu the
chaiacteis foi all of the othei tiansfoimation matiices you will see that (x,y)
E anu (z) A
1
as shown in iegion III of the table. Similai analysis can be
maue with iespect to iotations about x, y anu z.
Region IV Binary Products
This iegion list vaiious binaiy piouucts anu to which iiieuucible
iepiesentation that they belong. The uoibitals have the same symmetiy as
the binaiy piouucts. Foi example the u
xy
oibital tiansfoims the same as the
xy binaiy piouuct.
Writing Chemically Meaningful Representations
We will begin by consiueiing the symmetiy of moleculai vibiations. To a
goou appioximation, moleculai motion can be sepaiateu into tianslational,
iotational anu vibiational components.
Each atom in a molecule has thiee uegiees of fieeuom (motion) possible. An
entiie molecule theiefoie has SN uegiees of fieeuom foi N atoms.
S B0F aie foi tianslation in x, y anu z.
S B0F aie foi iotation in x, y anu z (note: lineai molecules can only iotate in 2
uimensions)
The iemain B0F aie vibiational in natuie
A molecule will have SN 6 possible vibiations
SN S foi lineai molecules
Intiouuction to the Chemical Applications of uioup Theoiy
Page 48
0sing the tools of classical mechanics it is possible to solve foi the eneigies of
all vibiations (think balls anu spiings mouel foi a molecule). The calculations
aie teuious anu complicateu anu as eaily as the 196us computeis have been
useu to uo the calculations.
1
Vibrations
We can use the tools of gioup theoiy to ueuuce the qualitative appeaiance of
the noimal moues of vibiation.
Well stait with a simple molecule like B
2
0.
Foi watei we expect SN6 = S noimal moues of vibiation. Watei is simple
enough that we can guess the moues.
symmetiic stietching antisymmetiic stietching benuing
Assign these thiee vibiations to iiieuucible iepiesentations in the C
2v
point
gioup.
C
2v
E C
2
(xz)
'
(yz)
A
1
1 1 1 1 z
A
2
1 1 1 1 R
z
B
1
1 1 1 1 x, R
y
B
2
1 1 1 1 y, R
x
Consiuei the uisplacement vectois (ieu aiiows) foi each moue anu wiite
what happens unuei each symmetiy opeiation.
1
Foi moie infoimation on these calculations, look up F anu u matiices in a gioup theoiy oi physical
chemistiy text. In summaiy this methou sums up anu solves all of the potential eneigies baseu on the foice
constants (bonu stiength) anu uisplacement vectois (vibiations). I =
1
2
k
s
s
k .k
wheie, f
ik
is the foice
constant anu s
i
anu s
k
aie uisplacements (stietching oi benuing). The teim f
ii
s
i
2
iepiesents the potential
eneigy of a puie stietch oi benu while the cioss teims iepiesent inteiactions between the vibiational moues.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 49
Symmetiic stietching (
1
)
E 1 , C
2
1,
(xz)
1,
'
(yz)
1
Anti Symmetiic stietching (
2
)
E 1 , C
2
1,
(xz)
1,
'
(yz)
1
Benuing (
S
)
E 1 , C
2
1,
(xz)
1,
'
(yz)
1
C
2v
E C
2
(xz)
'
(yz)
A
1
1 1 1 1 z
A
2
1 1 1 1 R
z
B
1
1 1 1 1 x, R
y
B
2
1 1 1 1 y, R
x
1
1 1 1 1
2
1 1 1 1
S
1 1 1 1
In a moie complicateu case we woulu apply the ieuuction foimula to finu the
iii
which compiise
1
A
1
2
B
1
S
A
1
A moie geneializeu appioach to finuing
cI
J
`
cI
N
i
J
cI
J
N
Wheie:
cI
is the electionic wavefunction anu
N
is the nucleai wavefunction
J
`
is the uipole moment opeiatoi
J
`
= (-e)r
+ Z
u
er
u
u
Wheie:
i
i
is the iauius vectoi fiom the oiigin to a chaige q
i
(an election in this case)
e is the pioton chaige
Z
is the nucleai chaige
i
th
funuamental vibiational level wavefunction.
What this all means is that a vibiational tiansition in the infiaieu iegion is
only alloweu if the vibiation causes a change in the uipole moment of the
molecule.
Bipole moments tianslate just like the Caitesian cooiuinate vectois x, y anu z.
Theiefoie only vibiations that have the same symmetiy as x, y oi z aie
alloweu tiansitions in the infiaieu.
Selection Rules for Raman Spectroscopy
In Raman spectioscopy, inciuent iauiation with an electiic fielu vectoi E
may
inuuce a uipole in a molecule. The extent of which uepenus on the
polaiizability of the molecule (o
]
polaiizability opeiatoi).
_
0
b
o
]
m
p
J
Tiansitions in Raman spectioscopy aie only alloweu if the vibiation causes a
change in polaiizability.
Polaiizability tiansfoims like the binaiy piouuct teims (xy, z
2
etc) anu
theiefoie vibiations that have the same symmetiy as the binaiy piouucts aie
alloweu tiansitions in Raman spectioscopy.
Foi watei, all thiee vibiations aie IR anu Raman active.
Intiouuction to the Chemical Applications of uioup Theoiy
Page S2
Normal Coordinate Analysis
Lets finu all of the vibiational moues foi watei in a systematic way. We
expect SN 6 = S vibiations.
A simple way to uesciibe all possible motions of a molecule is to consiuei a set
of thiee oithonoimal cooiuinates centeieu on each atom. Foi watei, this
iesults in a set of 9 vectois shown below. Any possible motion will be the sum
of all nine components.
Now, we will wiite the foui tiansfoimation matiices that iepiesent the
tiansfoimation of these nine vectois unuei the opeiations of the C
2v
point
gioup (E, C
2
,
v
(xz),
v
(yz))
Intiouuction to the Chemical Applications of uioup Theoiy
Page SS
E =
l
l
l
l
l
l
l
l
l
1 u u u u u u u u
u 1 u u u u u u u
u u 1 u u u u u u
u u u 1 u u u u u
u u u u 1 u u u u
u u u u u 1 u u u
u u u u u u 1 u u
u u u u u u u 1 u
u u u u u u u u 1
1
1
1
1
1
1
1
1
1
_ = 9
C
2
=
l
l
l
l
l
l
l
l
l
u u u u u u 1 u u
u u u u u u u -1 u
u u u u u u u u -1
u u u 1 u u u u u
u u u u -1 u u u u
u u u u u -1 u u u
1 u u u u u u u u
u -1 u u u u u u u
u u -1 u u u u u u
1
1
1
1
1
1
1
1
1
_ = -1
o
(xz) =
l
l
l
l
l
l
l
l
l
1 u u u u u u u u
u -1 u u u u u u u
u u 1 u u u u u u
u u u 1 u u u u u
u u u u -1 u u u u
u u u u u 1 u u u
u u u u u u 1 u u
u u u u u u u -1 u
u u u u u u u u 1
1
1
1
1
1
1
1
1
1
_ = S
o
(yz) =
l
l
l
l
l
l
l
l
l
u u u u u u 1 u u
u u u u u u u 1 u
u u u u u u u u -1
u u u 1 u u u u u
u u u u 1 u u u u
u u u u u -1 u u u
1 u u u u u u u u
u 1 u u u u u u u
u u -1 u u u u u u
1
1
1
1
1
1
1
1
1
_ = 1
Intiouuction to the Chemical Applications of uioup Theoiy
Page S4
The ieuucible iepiesentation that we have just foimeu is uenoteu
SN
, to
inuicate we have useu S oithonoimal vectois on each atom. Now that we
have the tiansfoimation matiices we can wiite the chaiacteis foi
SN
C
2v
E C
2
(xz)
'
(yz)
A
1
1 1 1 1 z
A
2
1 1 1 1 R
z
B
1
1 1 1 1 x, R
y
B
2
1 1 1 1 y, R
x
SN
9 1 S 1
The next step is to finu the lineai combination of iiieuucible iepiesentations
the compiise
SN
. We uo this by application of the ieuuction foimula to
SN
.
a
A
1
=
1
4
|(9)(1) + (-1)(1) + (S)(1) + (1)(1)] = S
a
A
2
=
1
4
|(9)(1) + (-1)(1) + (S)(-1) + (1)(-1)] = 1
a
B
1
=
1
4
|(9)(1) + (-1)(-1) + (S)(1) + (1)(-1)] = S
a
B
2
=
1
4
|(9)(1) + (-1)(-1) + (S)(-1) + (1)(1)] = 2
Intiouuction to the Chemical Applications of uioup Theoiy
Page SS
Lets finu all of the vibiational moues foi NB
S
. We expect SN 6 = 6
vibiations.
A simple way to uesciibe all possible motions of a molecule is to consiuei a set
of thiee oithonoimal cooiuinates centeieu on each atom. Foi NB
S
, this iesults
in a set of 12 vectois. Any motion will be the sum of all twelve components.
As peifoimeu pieviously foi a set of thiee x, y anu z vectois we can wiite a
tiansfoimation matiix that uesciibes what happens to each of the vectois foi
each symmetiy opeiation in the gioup.
We now neeu to finu the chaiacteis of
SN
C
Sv
E 2 C
S
S
v
A
1
1 1 1 z x
2
+y
2
, z
2
A
2
1 1 1 R
z
E 2 1 u (x,y)(Rx,Ry) (x
2
y
2
, xy)(xz,yz)
SN
. . .
The tiansfoimation matiices will be 1212. Bowevei, we aie only inteiesteu
in the chaiacteis () of each matiix. Foi E the chaiactei will be 12 since all
elements iemain unchangeu.
Intiouuction to the Chemical Applications of uioup Theoiy
Page S6
Consiuei a C
S
iotation:
0nly vectois on the N atom will go into _ themselves. Fiom oui pievious
iesults we know that x, y anu z tiansfoim like
-
1
2
S
2
u u u u u u u u u u
-
S
2
-
1
2
u u u u u u u u u u
u u 1 u u u u u u u u u
u u u u u u u 1 u u u u
u u u u u u -1 u u u u u
u u u u u u u u 1 u u u
u u u u u u u u u u 1 u
u u u u u u u u u -1 u u
u u u u u u u u u u u 1
u u u u -1 u u u u u u u
u u u 1 u u u u u u u u
u u u u u 1 u u u u u u
All othei components aie off uiagonal anu uo not contiibute to the chaiactei
of the matiix. Beie, = u foi C
S
.
Intiouuction to the Chemical Applications of uioup Theoiy
Page S7
Foi the veitical miiioi plane,
v
Foui vectois iemain unchangeu (on N anu B) anu two
go into 1 of themselves (on N anu B). The othei 6 on
the out of plane B atoms all become off uiagonal
elements.
= 2 (1+11+1+11+u+u+u+u+u+u)
Now we can wiite
SN
C
Sv
E 2 C
S
S
v
A
1
1 1 1 z x
2
+y
2
, z
2
A
2
1 1 1 Rz
E 2 1 u (x,y)(Rx,Ry) (x
2
y
2
, xy)(xz,yz)
SN
12 u 2
Apply the ieuuction foimula to finu what
iii
compiise
SN
o
=
1
b
_(R)
R
_
(R)
a
A
1
=
1
6
|(1)(1)(12) + (2)(1)(u) + (S)(1)(2)] = S
a
A
2
=
1
6
|(1)(1)(12) + (2)(1)(u) + (S)(-1)(2)] = 1
a
E
=
1
6
|(1)(2)(12) + (2)(-1)(u) + (S)(u)(2)] = 4
Intiouuction to the Chemical Applications of uioup Theoiy
Page S8
We wiite the following
3N
= S
A
1
A
2
4
L
Bowevei,
SN
uesciibes all possible motion, incluuing tianslation anu iotation.
Inspection of the chaiactei table ieveals that
tuns
=
A
1
L
ot
=
A
2
L
This leaves the vibiations as
b
= 2
A
1
2
L
notice we pieuicteu 6 noimal moues anu we have 6
uimensions iepiesenteu (two 11 anu two 22).
Now we will wiite pictuies iepiesenting what the vibiations look like.
A
1
is symmetiic with iespect to all opeiations
A
1
symmetiic stietching
A
1
symmetiic benuing
Intiouuction to the Chemical Applications of uioup Theoiy
Page S9
The E moues aie uegeneiate. That is they aie maue up of vibiations that aie
of equal eneigy.
L
asymmetiic stietching
The thiiu possible way of uiawing an asymmetiic stietch is just a lineai
combination of the two above (auu the two vibiations).
L
asymmetiic benuing
As with the stietches, the thiiu benu is foimeu fiom a lineai combination of
the othei two anu is not unique (subtiact the two benus).
Intiouuction to the Chemical Applications of uioup Theoiy
Page 6u
IR and Raman Spectra of CH
4
and CH
3
F
Nethane CB
4
belongs to the T
u
point gioup
Peifoim the noimal cooiuinate analysis foi methane anu ueteimine the
numbei anu symmetiy of all IR anu Raman active banus
Theie will be S(S)6 = 9 noimal moues of vibiation in both molecules
Noimal Cooiuinate Analysis of CB
4
1
st
wiite the chaiacteis foi
SN
T
u
E 8C
S
SC
2
6S
4
6
u
A
1
1 1 1 1 1 x
2
+y
2
+z
2
A
2
1 1 1 1 1
E 2 1 2 u u 2z
2
x
2
y
2
T
1
S u 1 1 1 (R
x
,R
y
,R
z
) x
2
y
2
T
2
S u 1 1 1 (x,y,z) (xy,xz,yz)
SN
1S u 1 1 S
Reuuce
SN
into its iiieuucible iepiesentations.
A
1
=
1
24
(1S + u - S - 6 + 18) = 1
A
2
=
1
24
(1S + u - S + 6 - 18) = u
L
=
1
24
(Su + u - 6 + u + u) = 1
1
1
=
1
24
(4S + u + S - 6 - 18) = 1
1
2
=
1
24
(4S + u + S + 6 + 18) = S
Intiouuction to the Chemical Applications of uioup Theoiy
Page 61
3N
=
A
1
L
T
1
S
1
2
tuns
=
1
2
anu
ot
=
1
1
Subtiacting the tianslational anu iotational iiieuucible iepiesentations we
aie left with
b
=
A
1
L
2
1
2
IR active moues aie the 6 moues in 2
1
2
All 9 moues aie Raman active
Calculateu IR anu Raman spectia foi CB
4
aie shown below
2
2
Spectia calculateu by uANESS using BaitieeFock methous
Intiouuction to the Chemical Applications of uioup Theoiy
Page 62
RamanSpectrum
1400 1600 1800 2000 2200 2400 2600 2800 3000 3200
Energy(cm-1)
0
1
I
n
t
e
n
s
i
t
y
Noimal Cooiuinate Analysis of CB
S
F
Now we peifoim the iuentical analysis foi CB
S
F which belongs to the C
Sv
point
gioup.
1
st
wiite the chaiacteis foi
SN
C
Sv
E 2C
S
S
v
A
1
1 1 1 z x
2
+y
2
, z
2
A
2
1 1 1 R
z
E 2 1 u (x,y) (R
x
,R
y
) (x
2
y
2
, xy)(xz,yz)
SN
1S u S
Reuuce
SN
into its iiieuucible iepiesentations.
A
1
=
1
6
(1S + u + 9) = 4
A
2
=
1
6
(1S + u - 9) = 1
L
=
1
6
(Su + u + u) = S
Intiouuction to the Chemical Applications of uioup Theoiy
Page 6S
3N
= 4
A
1
A
2
S
L
tuns
=
A
1
L
anu
ot
=
A
2
L
Subtiacting the tianslational anu iotational iiieuucible iepiesentations we
aie left with
b
= S
A
1
S
L
All 9 moues aie IR active
All 9 moues aie Raman active
Calculateu IR anu Raman spectia foi CB
S
F aie shown below
Intiouuction to the Chemical Applications of uioup Theoiy
Page 64
Alternate Basis Sets
To help uiaw pictuies of the vibiational moues we can use a basis set that
ielates moie uiiectly to vibiations, calleu inteinal cooiuinates. Foi CB
4
we
can use CB bonu stietches as a basis anu BCB benus as a basis.
T
u
E 8C
S
SC
2
6S
4
6
u
CB
4 1 u u 2 Stietches
BCB
6 u 2 u 2 benus
CH
=
A
1
1
2
HCH
=
A
1
L
1
2
If we auu this up we finu that this is 1u noimal moues but we expect only 9.
Looking at the benuing moues we see an A
1
iepiesentation. Since theie is no
way to inciease all the bonu angles at once in CB
4
this must be uiscounteu.
In oiuei to visualize the vibiations be must make lineai combinations of oui
basis set elements that aie oithonoimal (symmetiy auapteu).
Intiouuction to the Chemical Applications of uioup Theoiy
Page 6S
Projection Operator
The piojection opeiatoi allows us to finu the symmetiy auapteu lineai
combinations we neeu to visualize the vibiational moues in CB
4
anu CBB
S
.
P
`
I
= _
l
b
] _
(R)(R
`
)
R
Wheie
l
1
=
1s
A
+
1s
B
1
=
1s
A
-
1s
B
Intiouuction to the Chemical Applications of uioup Theoiy
Page 72
Constiuctive inteifeience leaus to the N0 shown in the top example anu the
iesulting N0 is saiu to be bonuing. Bestiuctive inteifeience gives the seconu
example is teimeu antibonuing.
Foi 0
2
the N0 uiagiam is shown below. This coiiectly pieuicts that 0
2
has
two unpaiieu elections. None of the pievious theoiies coulu accommouate foi
this fact.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 7S
Quantum mechanical description of orbitals
Eiwin Schiouingei pioposeu a methou to finu election wavefunctions. The
timeinuepenuent Schiouingei equation in one uimension is
-
l
2
2m
J
2
Jx
2
+ I(x) = E
wheie is the wavefunction anu
l =
b
2n
= 1.uS4 1u
-34
v(x) is the potential eneigy of the election at position x anu
anu -
l
2
2m
d
2
dx
2
is the kinetic eneigy of the election. This equation is often
simplifieu as
J
= E
wheie J
= J
R
Theie aie cases in which multiple Eigen functions give the same Eigen value.
J
1
= E
1
J
2
= E
2
:
J
n
= E
n
We say that the Eigen value is uegeneiate oi nfolu uegeneiate. In these cases
the Eigen functions aie a solution to the Schiouingei equation anu also any
lineai combination of the uegeneiate Eigen functions
J
o
]
]
= E
o
]
]
] ]
We will constiuct the Eigen functions (anu subsequently the lineai
combinations) so that they aie all oithonoimal to each othei.
_
]
J = o
]
The set of oithonoimal Eigen functions foi a molecule can foim the basis of an
iiieuucible iepiesentation of the gioup. Foi a nonuegeneiate Eigen function
we have
J
= E
so that R
i
is an Eigen function of the Bamiltonian.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 7S
Because
i
is noimalizeu R
i
= _ 1
i
. Theiefoie if we apply all R in a gioup
to a nonuegeneiate
i
, we get a iepiesentation weie each matiix element,
i
(R) will be _ 1. A oneuimensional matiix is by uefinition iiieuucible.
A similai analysis foi nfolu uegeneiate Eigen functions will iesult in an n
uimensional iiieuucible iepiesentation.
Bow uo we finu the lineai combination of wavefunctions that iesult in a set of
oithonoimal Eigen functions.
The piojection opeiatoi uiscusseu pieviously foi vibiational analysis is useful
again heie.
P
`
I
i
= _
l
b
] _
(R)(R
`
)
R
Constiuction of basis sets to pioject is the subject of theoietical chemistiy anu
physics. Because we cannot solve the Schiouingei equation uiiectly we must
make appioximations.
BaitieeFock Appioximation wiite N0s foi each election inuepenuently of
the otheis. The eiioi that is intiouuceu heie is that the election position
uepenus on the position of all of the othei elections (electionelection
iepulsion). A coiiection factoi must be applieu aftei solving the pioblem to
account foi this. This is calleu the coiielation eneigy.
Rules foi Noleculai 0ibitals
1) Wavefunctions cannot uistinguish between elections
2) If elections exchange positions, the sign of the wavefunction must
change.
LCAO Approximation
Noleculai 0ibitals aie lineai combinations of atomic oibitals.
electron Approximation
assume that anu bonus aie inuepenuent of each othei. That is, bonus
aie localizeu, while bonus may be uelocalizeu.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 76
Hckel Orbital Method
We will use a ieuefineu Bamiltonian calleu the effective Bamiltonian.
E
c]],n
(p) = b
coc
+ {2[
(p) - K
(p)]
wheie } anu K aie the Coulomb anu exchange integials iespectively. The
Coulomb integial takes into account the electionelection iepulsion between
two elections in uiffeient oibitals, anu the exchange integial ielates to the
eneigy when elections in two oibitals aie exchangeu with each othei.
S
In the Bckel oibital methou we constiuct new N0s as follows
n
(k) = C
s]
s
(k)
N
s=1
wheie N is the numbei of atoms in the oibital system,
s
is a p
z
oibital on a
given atom anu C
sj
is a coefficient (ueteimineu by piojection).
Bckel theoiy makes the following appioximations:
E
c]],n
= o
E
s
c]],n
= _
[ (if i anu s aie neaiest neighbois)
u (otheiwise)
is the Coulombic integial which iaises the eneigy of a wavefunction
(positive value) anu is the iesonance integial which loweis the eneigy of a
wavefunction (negative value). These integials can be evaluateu numeiically
but aie beyonu the scope of what we hope to accomplish heie.
S
S
Foi moie infoimation on bonuing theoiy consult an appiopiiate text on quantum
mechanics.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 77
As it stanus so fai, we have a methou foi finuing the eneigies of N oibitals
foi N atoms. The iesult is an Nuimensional polynomial. Pioblems of this type
can be solveu but application of symmetiy to the system gieatly ieuuces the
amount of woik to be uone.
Hckel Orbitals for Nitrite
Consiuei the oibital system foi the nitiite anion (N0
2
-
)
This molecule belongs to the C
2v
point gioup. We will use a p
z
oibital on each
atom to constiuct the oibital system foi nitiite. This foims the basis foi a
ieuucible iepiesentation,
A0
We must wiite the chaiacteis foi
A0
in an analogous mannei as we wiote the
chaiacteis foi
SN
. Keep in minu the sign of the wavefunctions when
peifoiming the symmetiy opeiations.
C
2v
E C
2
(xz)
'
(yz)
A
1
1 1 1 1
A
2
1 1 1 1
B
1
1 1 1 1
B
2
1 1 1 1
A0
S 1 1 S
Intiouuction to the Chemical Applications of uioup Theoiy
Page 78
Next we ieuuce
A0
to finu the iiieuucible components.
o
A
1
=
1
4
|(1)(S) + (1)(-1) + (1)(1) + (1)(-S)] = u
o
A
2
=
1
4
|(1)(S) + (1)(-1) + (-1)(1) + (-1)(-S)] = 1
o
B
1
=
1
4
|(1)(S) + (-1)(-1) + (1)(1) + (-1)(-S)] = 2
o
B
2
=
1
4
|(1)(S) + (-1)(-1) + (-1)(1) + (1)(-S)] = u
A0
=
A
2
2
B
1
Next we pioject the basis functions out of the iiieuucible iepiesentations.
Because
1
anu
S
aie equivalent it uoesnt mattei which one we pick.
Bowevei,
2
is unique anu must also be piojecteu each time.
P
I
A
2
(
1
) =
1
4
(
1
-
3
-
3
+
1
) =
1
2
(
1
-
3
)
P
I
B
1
(
2
) =
1
4
(
2
-
2
-
2
+
2
) = u (i.e. no contiibution)
P
I
B
1
(
1
) =
1
4
(
1
+
3
+
3
+
1
) =
1
2
(
1
+
3
)
P
I
B
1
(
2
) =
1
4
(
2
+
2
+
2
+
2
) =
2
Theie aie two oibitals with B
1
symmetiy. So we will take lineai combinations
of the two piojecteu oibitals to finu the oithogonal iesults
1
=
1
2
(
1
-
3
)
2
=
1
2
1
+
2
+
1
2
3
=
1
2
1
-
2
+
1
2
3
Intiouuction to the Chemical Applications of uioup Theoiy
Page 79
Lastly we must noimalize the oibitals since it is assumeu that
_
]
J = o
]
Theie is a noimalization factoi N that is founu as follows foi
1
_N
1
2
(
1
-
3
)
N
1
2
(
1
-
3
)J = 1
1
4
N
2
_(
1
-
3
)
(
1
-
3
)J = 1
1
4
N
2
_(
1
-
3
)
(
1
-
3
)J = 1
2
]=1
2
=1
Note that the sums heie give
ij
foi the inuiviuual
i
j
teims. Theie aie foui
integials in this case involving oveilap of <
1,
1
> , <
1,
S
> , <
S,
1
> ,
<
S,
S
>. These give 1 + u + u + 1 iespectively.
1
4
N
2
2 = 1
solving foi N we finu N = 2 oui noimalizeu
1
is then
1
=
2
2
(
1
-
3
) (A
2
symmetiy)
Noie geneially foi a noimalizeu wavefunction has the foim
= N
o
]
]
]
anu we know noimalizeu wavefunctions follow;
_
I
I
J = 1
Intiouuction to the Chemical Applications of uioup Theoiy
Page 8u
Theiefoie;
1
N
2
= _(o
]
]
)
2
J
1
N
2
= (o
]
)
2
_(
]
)
2
J
_______
1
The integial in the above expiession must evaluate to 1 since the basis
functions
j
aie oithonoimal wavefunctions.
Solving foi the noimalization factoi N
i
gives;
N
=
1
_
o
]
2
]
Applying this to
2
above we finu,
2
=
1
2
1
+
2
+
1
2
3
anu N
=
1
_
[
1
2
2
+1
2
+[
1
2
2
=
1
_
3
2
= _
2
3
anu the noimalizeu wavefunction becomes;
2
= _
2
3
[
1
2
1
+
2
+
1
2
3
(B
1
symmetiy)
Similaily we finu the noimalizeu
S
to be
3
= _
2
3
[
1
2
1
-
2
+
1
2
3
(B
1
symmetiy)
Intiouuction to the Chemical Applications of uioup Theoiy
Page 81
If we evaluate E
c]],n
foi each new oibital we finu that
E
(4
1
4
1
)
c]],n
= _
2
2
(
1
-
3
)
E
c]],n
2
2
(
1
-
3
)J
Bistiibuting the
i
acioss the Bamiltonian anu sepaiating the integials we aie
left with the following sum
_
2
2
(
1
)
E
c]],n
2
2
(
1
)J + _
2
2
(
1
)
E
c]],n
2
2
(-
3
)J +_
2
2
(-
3
)
E
c]],n
2
2
(
1
)J +_
2
2
(-
3
)
E
c]],n
2
2
(-
3
)J
These integials evaluate accoiuing to Bckel appioximations as
E
(4
1
4
1
)
c]],n
=
1
2
o + u + u +
1
2
o
Simplifying leaves us with:
E
(4
1
4
1
)
c]],n
=
1
2
(o + o) = o
A similai analysis foi
2
anu
S
yielus:
E
(4
2
4
2
)
c]],n
=
2
3
[
1
4
o +
1
2
[ +
1
2
[ + o +
1
2
[ +
1
2
[ +
1
4
o = o +
4
3
[
E
(4
3
4
3
)
c]],n
=
2
3
[
1
4
o -
1
2
[ -
1
2
[ + o -
1
2
[ -
1
2
[ +
1
4
o = o -
4
3
[
In oiuei of incieasing eneigy we finu
2
<
1
<
S
Recall that is a negative teim anu loweis the eneigy of the oibital.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 82
Biawing pictuies of the oibitals helps to visualize the iesults
B
1
antibonuing oibital
o -
4
S
[
A
2
nonbonuing oibital
o
B
1
bonuing oibital
o +
4
S
[
Intiouuction to the Chemical Applications of uioup Theoiy
Page 8S
Nitiite oibitals calculateu using ab initio methous.
B
1
antibonuing oibital
A
2
nonbonuing oibital
B
1
bonuing oibital
Intiouuction to the Chemical Applications of uioup Theoiy
Page 84
Hckel MOs for Cyclobutadiene
Finu the oibitals foi cyclobutauiene using the Bckel oibital methou.
Cyclobutauiene belongs to the B
4h
point gioup. This gioup has an oiuei of 16.
To ieuuce the woik, we can use a subgioup of B
4h
, B
4
which has an oiuei of 8.
In uoing so we lose infoimation about the ouu oi even natuie of the oibital (g
oi u). Bowevei, once the N0s aie constiucteu we can easily ueteimine an
N0s g oi u status thiough examination of symmetiy opeiations on the new
N0s.
The basis set will be the foui p
z
oibitals peipenuiculai to the moleculai plane.
Wiiting
A0
foi B
4
we finu;
B
4
E 2C
4
C
2
2C
2
2C
2
A
1
1 1 1 1 1
A
2
1 1 1 1 1
B
1
1 1 1 1 1
B
2
1 1 1 1 1
E 2 u 2 u u
A0
4 u u 2 u
Reuucing
A0
iesults in
A0
=
A
2
B
2
L
Intiouuction to the Chemical Applications of uioup Theoiy
Page 8S
Now we must pioject out the symmetiy auapteu lineai combinations anu
then noimalize the iesulting functions.
P
I
A
2
(
1
) =
1
8
(
1
+
2
+
4
+
3
+
1
+
3
+
2
+
4
)
1
=
1
4
(
1
+
2
+
3
+
4
)
P
I
B
2
(
1
) =
1
8
(
1
-
2
-
4
+
3
+
1
+
3
-
2
-
4
)
2
=
1
4
(
1
-
2
+
3
-
4
)
P
I
E
(
1
) =
2
8
(2
1
- 2
3
) =
1
2
(
1
-
3
)
Because E is twouimensional, we must pioject an auuitional oibital.
P
I
E
(
2
) =
2
8
(2
2
- 2
4
) =
1
2
(
2
-
4
)
The two E N0s will be the lineai combination (sum anu uiffeience) of the two
piojections we have just maue.
3
=
1
2
(
1
+
2
-
3
-
4
)
4
=
1
2
(
1
-
2
-
3
+
4
)
Intiouuction to the Chemical Applications of uioup Theoiy
Page 86
Noimalizing the N0s iesults in the following oithonoimal set of functions
1
=
1
2
(
1
+
2
+
3
+
4
) A
2
symmetiy
2
=
1
2
(
1
-
2
+
3
-
4
) B
2
symmetiy
3
=
1
2
(
1
+
2
-
3
-
4
) E symmetiy
4
=
1
2
(
1
-
2
-
3
+
4
) E symmetiy
To put the oibital in the coiiect oiuei eneigetically, we evaluate E
c]],n
foi
each N0.
E
(4
1
4
1
)
c]],n
= o + 2[
E
(4
2
4
2
)
c]],n
= o - 2[
E
(4
3
4
3
)
c]],n
= o
E
(4
4
4
4
)
c]],n
= o
Because the E oibital is uegeneiate, both oibitals must have the same eneigy.
We finu the in oiuei of incieasing eneigy,
1
<
S
,
4
<
2
.
Lastly we can look at how the each of these oibitals tiansfoims in the B4h
point gioup anu assign the g oi u subsciipt. Foi example, the B
2
oibital coulu
be B
2u
oi B
2g
. 0nuei inveision (i) the oibital goes into 1 of itself so it must be
B
2u
(the chaiactei unuei i foi B
2g
is +1 anu 1 foi B
2u
). Analysis of the
iemaining oibits gives A
2u
anu E
g
.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 87
B
2u
antibonuing
o - 2[
E
g
bonuing
o
A
2u
bonuing
o + 2[
moleculai oibitals as calculateu by ab initio methous
B
2u
E
g
A
2u
Intiouuction to the Chemical Applications of uioup Theoiy
Page 88
A note of caution. We might be tempteu to view cyclobutauiene as an
aiomatic iing system baseu upon the appeaiance of the A
2u
oibital.
Bowevei, examination of the election uensity coloi mappeu with the
electiostatic potential (ieu = negative, blue = positive) ieveals a nonunifoim
election uensity uistiibution. This inuicates that cyclobutauiene is not
aiomatic but iathei alteinating uouble anu single bonus.
If the stiuctuie is geometiy optimizeu, we see that the symmetiy is no longei
B
4h
, but iathei that of a iectangle, B
2h
. The electiostatic potential map places
extia election uensity along the shoitei uouble bonus we woulu pieuict. The
Bckel iule foi aiomaticity iequiies 4n + 2 elections anu heie we have only
4 elections, so the lack of aiomaticity is expecteu.
If the symmetiy changes, the symmetiy of the moleculai oibitals also changes.
Calculations of the new oibitals aie shown on the following page.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 89
Ab initio calculations foi the oibitals in geometiy optimizeu cyclobutauiene.
A
u
B
Sg
B
2g
B
1u
Notice that the geneial shape of the N0s is similai to what we calculateu foi
the molecule unuei B
4h
symmetiy, but the E
g
oibital has split into the non
uegeneiate B
2g
anu B
Sg
oibitals shown above.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 9u
Hckel MOs for Boron Trifluoride
B
Sh
E 2C
S
SC
2
h
2S
S
S
v
A
1
1 1 1 1 1 1
A
2
1 1 1 1 1 1
E 2 1 u 2 1 u
A
1
1 1 1 1 1 1
A
2
1 1 1 1 1 1
E 2 1 u 2 1 u
Constiuct the Bckel moleculai oibitals foi caibonate anu compaie to the
iesults foi semiempiiical calculations of all moleculai oibitals foi caibonate.
Step 1. Finu
A0
B
Sh
E 2C
S
SC
2
h
2S
S
S
v
A0
4 1 2 4 1 2
Step 2. Apply the ieuuction foimula to finu the iiieuucible iepiesentations.
o
A
1
| =
1
12
(4 + 2 - 6 - 4 - 2 + 6) = u
o
A
2
| =
1
12
(4 + 2 + 6 - 4 - 2 - 6) = u
o
L
|| =
1
12
(8 - 2 + u - 8 + 2 + u) = u
o
A
1
|| =
1
12
(4 + 2 - 6 + 4 + 2 - 6) = u
o
A
2
|| =
1
12
(4 + 2 + 6 + 4 + 2 + 6) = 2
o
L
|| =
1
12
(8 - 2 + u + 8 - 2 + u) = 1
A0
= 2
A
2
||
L
||
Intiouuction to the Chemical Applications of uioup Theoiy
Page 91
Step S. Pioject the new N0s
Because
1
is on the centei atom we must pioject
1
anu one of the otheis anu
make lineai combinations to be suie to have complete oibitals.
P
I
A
2
||
(
1
) =
1
12
(
1
+
1
+
1
+
1
+
1
+
1
+
1
+
1
+
1
+
1
+
1
+
1
) =
1
P
I
A
2
||
(
2
) =
1
12
(
2
+
3
+
4
+
2
+
3
+
4
+
2
+
3
+
4
+
2
+
3
+
4
)
=
1
S
(
2
+
3
+
4)
Taking the lineai combinations of these two we obtain the following:
1
=
1
+
1
S
2
+
1
S
3
+
1
S
2
=
1
-
1
S
2
-
1
S
3
-
1
S
4
Noimalizing these iesults gives:
1
=
S
2
(
1
+
1
S
2
+
1
S
3
+
1
S
4
)
2
=
S
2
(
1
-
1
S
2
-
1
S
3
-
1
S
4
)
Now pioject the E oibitals
P
L
||
(
1
) =
1
12
(2
1
-
1
-
1
+ 2
1
-
1
-
1
) = u
Because
1
uoes not contiibute to the E oibital we must pioject two othei
basis functions anu take theii lineai combinations.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 92
P
L
||
(
2
) =
2
12
(2
2
-
3
-
4
+ 2
2
-
3
-
4
) =
1
6
(2
2
-
3
-
4
)
P
L
||
(
3
) =
2
12
(2
3
-
4
-
2
+ 2
3
-
4
-
2
) =
1
6
(2
3
-
4
-
2
)
3
=
1
6
(
2
+
3
- 2
4
)
4
=
1
6
(S
2
- S
3
)
Aftei noimalization we aie left with
3
=
1
6
(
2
+
3
- 2
4
)
4
=
1
2
(
2
-
3
)
Step 4. Beteimine the eneigy of each oibital by evaluating B
eff,
.
E
(4
1
4
1
)
c]],n
=
S
4
_o +
1
S
[ +
1
S
[ +
1
S
[ +
1
9
o +
1
S
[ +
1
9
o +
1
S
[ +
1
9
o +
1
S
[]
= o +
S
2
[
E
(4
2
4
2
)
c]],n
=
S
4
_o -
1
S
[ -
1
S
[ -
1
S
[ +
1
9
o -
1
S
[ +
1
9
o -
1
S
[ +
1
9
o -
1
S
[]
= o -
S
2
[
E
(4
3
4
3
)
c]],n
=
1
6
(o + o + 4o) = o
E
(4
4
4
4
)
c]],n
=
1
2
(o + o) = o
Intiouuction to the Chemical Applications of uioup Theoiy
Page 9S
Step S. Constiuct the N0 uiagiam anu uiaw pictuies of the N0s
A
2
( o -
3
2
[)
E( o)
A
2
( o +
3
2
[)
These sketches aie a topuown view. The sign of the wavefunction is opposite
on the bottom siue.
Intiouuction to the Chemical Applications of uioup Theoiy
Page 94
Ab initio calculations give the following N0 pictuies anu the coiiesponuing
eneigy (in Baitiee).
A
2
u.u418 Ba
E
-u.9u7S Ba
A
2
-u.9411 Ba
Intiouuction to the Chemical Applications of uioup Theoiy
Page 9S
One final exercise
1. Constiuct the oithonoimal Bckel moleculai oibitals foi benzene
using the subgioup B
6
(given below) anu a basis set of the six p
z
oibitals
that lie peipenuiculai to the plane of the iing.
2. Beteimine the coiiect oiueiing of the N0s eneigetically anu constiuct
the N0 uiagiam foi the system. Refei to the full B
6h
point gioup
chaiactei table to assign g anu u uesignations to the oibitals.
S. Sketch each of the six oibitals. Compaie youi iesults to the ab initio
calculations on the following page.
B
6
E 2 C
6
2 C
S
C
2
S C
2
S C
2
A
1
1 1 1 1 1 1
A
2
1 1 1 1 1 1
B
1
1 1 1 1 1 1
B
2
1 1 1 1 1 1
E
1
2 1 1 2 u u
E
2
2 1 1 2 u u
A0
Intiouuction to the Chemical Applications of uioup Theoiy
Page 96
Ab initio calculations foi the oibitals of benzene aie shown below
B
2g
u.S48u Ba
E
2u
u.1S22 Ba
E
1g
u.SS96 Ba
A
2u
u.Su7S Ba