Group Theory - Lecture Notes

Couise Lectuie Notes
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 (ISBN-1S: 978-u-486-67SSS-4) anu Chemical Applications
of uioup Theoiy by F. Albeit Cotton (ISBN-1u: u-471-17S7u-6).

Pictuies of Noleculai oibitals weie obtaineu fiom inteinet souices as follows:

Caibonate oibitals
0niveisity of Lethbiiuge
http:classes.uleth.ca2uu8uSchem2uuuachem2uuu_pioblems_u2_answeis.puf

Benzene oibitals
Technical 0niveisity of Baimstaut
http:csi.chemie.tu-
uaimstaut.ueakimmelsciiptieuiiect.cgi.filename=http:csi.chemie.tu-
uaimstaut.ueakimmeltutoiialsoibitalsmoleculaibenzene.html

See also foi oiganic N0s anu hybiiu oibital systems.
http:csi.chemie.tu-uaimstaut.ueakimmelinuex.html (click the tutoiials link)
Theie aie many SB vRNL mouels that can be iotateu in ieal time on youi web biowsei.

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


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

Page 4
Bomewoik Set 1.......................................................................................................................... 22
Point uioups ................................................................................................................................. 2S
Classification of Point uioups ............................................................................................... 24
Systematic Nethou to Assign Point uioups .................................................................... 2S
Classes in Symmetiy Point uioups ..................................................................................... 27
Bomewoik Set 2.......................................................................................................................... 29
Piopeities of Natiices .............................................................................................................. Su
Natiix math basics ..................................................................................................................... Su
Auuition anu Subtiaction ................................................................................................ Su
Natiix multiplication ........................................................................................................ S1
Natiix Bivision .................................................................................................................... S1
Special Natiices ................................................................................................................... S2
Natiix Repiesentations of Symmetiy 0peiations........................................................ SS
Iuentity .................................................................................................................................... SS
Reflection ............................................................................................................................... SS
Inveision................................................................................................................................. SS
Rotation .................................................................................................................................. S4
Impiopei Rotations ........................................................................................................... SS
vectois anu Scalai Piouucts .................................................................................................. S7
Repiesentations of uioups ..................................................................................................... S8
The uieat 0ithogonality Theoiem ...................................................................................... 4u
Iiieuucible Repiesentations .................................................................................................. 41
The Reuuction Foimula ........................................................................................................... 46
Chaiactei Tables ......................................................................................................................... 48
Region I Nulliken Symbols foi Iiieuucible Repiesentations ............................... 48
Region II Chaiacteis .............................................................................................................. 49
Region III Tianslations anu Rotations ........................................................................... 49

Page S
Region Iv Binaiy Piouucts ................................................................................................... 49
Wiiting Chemically Neaningful Repiesentations ......................................................... Su
vibiations ...................................................................................................................................... Su
Selection Rules foi vibiations ............................................................................................... SS
Selection Rules foi Raman Spectioscopy ......................................................................... S4
Noimal Cooiuinate Analysis .......................................................................................... SS
IR anu Raman Spectia of CB
4
anu CB
S
F ............................................................................ 6u
Bomewoik Set S.......................................................................................................................... 6S
Piojection 0peiatoi ................................................................................................................... 66
Bonuing Theoiies ....................................................................................................................... 69
Lewis Bonuing Theoiy ............................................................................................................. 69
vSEPR valence Shell Election Paii Repulsion Theoiy ............................................ 69
valance Bonu Theoiy ................................................................................................................ 7u
Bybiiu 0ibital Theoiy .............................................................................................................. 71
Noleculai 0ibital Theoiy ........................................................................................................ 72
Quantum mechanical uesciiption of oibitals .......................................................... 7S
uioup Theoiy anu Quantum Nechanics ........................................................................... 7S
LCA0 Appioximation ................................................................................................................ 76
election Appioximation ...................................................................................................... 76
Bckel 0ibital Nethou ......................................................................................................... 77
Bckel 0ibitals foi Nitiite ...................................................................................................... 78
Bckel N0s foi Cyclobutauiene .......................................................................................... 84
Bckel N0s foi Boion Tiifluoiiue ..................................................................................... 9u
Bomewoik Set 4 Final Exam .............................................................................................. 9S


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
(1811-18S2) 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 (1849-1917)
Eaily chemical applications to quantum mechanics came fiom the woik of
Beimann Weyl (188S-19SS) anu Eugene Wignei (19u2-199S)

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


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 n-folu 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.

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.

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.


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.


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,S-tiihyuioxybenzene (planai) CS
h

E, 2C
S
,
h
2S
S

Theie is an S
3
1
anu an S
3
5
(also calleu S
3
-1
)


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


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)

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


Page 1S
Consiuei the ammonia molecule (C
Sv
)
E, SC
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


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


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
_
A
k
B
k]
= (AB)
]
n
k

A
ik
=element in the i
th
iow anu k
th
column

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 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.


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.


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..

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.


Page 22
Homework Set 1

NANE :

(1) Below is one of the two possible gioup multiplication tables of oiuei 6, u
6
(1)
. Wiite the
gioup multiplication table foi u
6
(2)
.

Keep in minu the ieaiiangement theoiem when builuing the new table.
The iesult of multiplication of XY is the inteisection of the X column anu they Y iow so
that BC = F anu CB = B in the given table below. Bint, the gioup u
6
(2)
is a cyclic gioup.

u
6
(1)

E A B C B F
u
6
(2)

E A B C B F
E E A B C B F E
A A E B F B C A
B B F E B C A B
C C B F E A B C
B B C A B F E B
F F B C A E B F

(2) Iuentify all of the subgioups within u
6
(2)
anu wiite theii gioup
multiplication tables.


Page 2S
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
C
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
.


Page 24
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
Shoenflies 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


Page 2S
Systematic Method to Assign Point Groups


Page 26
Assign the point gioups to the following molecules
i only C
i

B
C
n
C
S
C
Sh
C
Sv


Page 27
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


Page 28

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


Page 29

Homework Set 2
1. List all of the symmetiy opeiations anu symmetiy elements foi the following
molecules. List the opeiations that commute with each othei. Excluue E which
always commutes with eveiy element - Foi example in watei you coulu wiite
C
2
v
(xy) =
v
(xy)C
2
, wheie
v
(xy) is the miiioi plane containing the B-0-B atoms.
v
(xz) is the miiioi plane containing only the 0 atom.

2. Constiuct the gioup multiplication table foi the symmetiy opeiations of watei.

S. Assign the following sets of geometiic isomeis to theii iespective point gioups
(ignoie any hyuiogen atoms when assigning the gioup) .

4. Bow many classes aie in the point gioup assigneu to sulfui choloipentafluoiiue.

Page Su
Properties of Matrices

Natiix: iectangulai aiiay of numbeis oi elements
_
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


Page S1
Matrix multiplication
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
_


Page S2
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
_
u
= o
]] ]
This is the sum of the uiagonal elements of a matiix (tiace).
a
is call the chaiactei of a matiix
piopeities of
if c = ab anu u = ba then
c
=
u
conjugate matiices have iuentical
i = b
-1
pb then
i
=
b

0peiations that aie in the same class have the same chaiactei.


Page SS
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
_


Page S4
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
_


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 is founu by exchanging iows into columns (taking the tianspose of
the matiix).
Consiuei a C
S
iotation about the z-axis.
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


Page S6

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 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 fiom 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.

Page S7
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

0sing a tiig iuentity we can wiite

Page S8
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
foi n-uimensional space

n
=1

0ithogonal vectois aie uefineu as those in which the following is tiue
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


Page S9
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. E
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.

Page 4u

The Great Orthogonality Theorem
The theoiem states
|
(R)
mn
]|
]
(R)
m
|
n
|]
R
=
l
]
o
]
o
mm
| o
nn
|
Teims
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
| ]
= complex conjugate of the element in the m

th
iow anu n
th

column of an opeiatoi R in iepiesentation
]

What uoes this all mean.
Foi any two iiieuucible iepiesentations

,
]

Any coiiesponuing matiix elements (one fiom each matiix) behave as
components of a vectoi in h-uimensional space, such that all vectois aie
oithonoimal. That is, oithogonal anu of unit length.


Page 41

Examine the theoiem unuei vaiious conuitions
If vectois aie fiom uiffeient iepiesentations then they aie oithogonal
|
(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
=

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
=

2) The sum of the squaies of the chaiacteis in an iiieuucible
iepiesentation is equal to the oiuei of the gioup

Page 42
|_
(R)]
2
=

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


Page 4S
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.

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

1
2
= (11) + (1-1) + (1-1) +(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

Page 44
C
Sv
E 2C
S
S
v

1
1 1 1
2
1 1 -1

1
2
= (11) + 2(1-1) + S(1-1) = u
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 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

Page 4S
B
1
1 -1 1 -1 E 2 -1 u
B
2
1 1 -1 -1

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) = o
]

Foi each sum ovei j we have
o
]
_
]
(R)
R
_
(R) = o
]
_
]
(R)
R
_
(R) = o
]
o
]


Page 46
The chaiacteis foi
i
anu
j
foim oithogonal vectois we can only have non-
zeio values when i j

The Reduction Formula

The above leaus to the impoitant iesult calleu The Reuuction Foimula
o
=
1
_(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


Page 47
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

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


Page 48

Character Tables
Foi C
Sv
we finu the following chaiactei table with foui iegions.
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)
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
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 anti-symmetiic 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 anti-symmetiic (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 anti-symmetiic
()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.

Page 49
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 Rx, Ry, Rz 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
_
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 u-oibitals have the same symmetiy as
the binaiy piouucts. Foi example the u
xy
oibital tiansfoims the same as the
xy binaiy piouuct.

Page Su
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
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.

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.

Page S1
Foi watei we expect SN-6 = S noimal moues of vibiation. Watei is simple
enough that we can guess the moues.

symmetiic stietching anti-symmetiic 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.
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


Page S2

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
. Bowevei, in this case we see by inspection that
1
A
1

2
B
1

S
A
1

A moie geneializeu appioach to finuing
will be uiscusseu latei.


Page SS
Selection Rules for Vibrations
Boin-0ppenheimei appioximation: elections move fast ielative to nucleai
motion.
=
cI
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
`
= (c)r
+Z
u
cr
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
is the iauius vectoi foi a nucleus

Integials of this type uefine the oveilap of wavefunctions. When the above
integial is not equal to u, a vibiational tiansition is saiu to be alloweu. That is,
theie exists some uegiee of oveilap of the two wavefunctions allowing the
tiansition fiom one to the othei.
In 18uu Sii William Beischel put a theimometei in a uispeiseu beam of light.
When he put the theimometei into the iegion beyonu the ieu light he noteu
the tempeiatuie incieaseu even moie than when placeu in the visible light.
Be hau uiscoveieu infiaieu (IR) light.


Page S4
Similai to electionic tiansitions with visible anu 0v light, IR can stimulate
tiansitions fiom
1

2
. A simplifieu integial uesciibing this tiansition is
_
0
b
J
`

m
p
J
which is alloweu when the integial uoes not equal zeio.
In this integial
0
b
= vibiational giounu state wavefunction anu
m
p
is the
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.


Page SS
Normal Coordinate Analysis
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 Rz
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.

Consiuei a C
S
iotation:

Page S6
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
.


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
_(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


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
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


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).


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


Page 61

3N
=
A
1
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 Baitiee-Fock methous

Page 62
Raman Spectrum
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


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
T
r
a
n
s
m
i
t
t
a
n
c
e
(
%
)


Page 64
I
n
t
e
n
s
i
t
y

Alternate Basis Sets
To help uiaw pictuies of the vibiational moues we can use a basis set that
ielates to vibiations. 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
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).


Page 6S
Homework Set 3
1. Constiuct the set of SS matiices that tiansfoim a set of {x,y,z} cooiuinates foi the
following opeiations : E, C
2
, i,
h
. Show that these matiices foim a ieuucible
iepiesentation of the C
2h
point gioup.

2. Consiuei the following molecule (tetiachloioplatinate)
Cl
Pt
Cl
Cl Cl

Wiite the chaiacteis foi
SN
Finu all of the iiieuucible iepiesentations that foim
SN
Inuicate which iiieuucible iepiesentation coiiesponu to
tian
,
iot
anu
vib
Bow many vibiations aie infiaieu active anu what aie theii symmetiies.
Bow many vibiations aie Raman active anu what aie theii symmetiies.

S. Byuiogen peioxiue (B
2
0
2
) is non-planai with both B atoms lying above the plane.
0 0
B
B

Assign the point gioup anu ueteimine the symmetiy of the vibiations foi this
molecule.

Sketch what the vibiations might look like. Aftei youve finisheu, check youi iesults
using the SBNoimalNoues piogiam (link on the couise website). Bow well uo youi
pieuictions match.


Page 66
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
] _
(R)(R
`
)
R

Wheie
l
= the uimension of the iiieuucible iepiesentation

i
= the oiuei of the gioup
_
(R)= chaiactei of opeiation R

R
`
= iesult of the symmetiy opeiation R on a basis function
Pioject out the A
1
moue foi methane (iecall
CH
=
A
1
1
2
)
T
u
E 8C
S
SC
2
6S
4
6
u

A
1
1 1 1 1 1

Now we must label oui basis functions anu keep tiack of what happens to
them unuei each opeiation.
P
`
A
1
(v
1
) =
1
24
(v
1
+v
1
+v
1
+v
2
+ v
3
+v
3
+v
4
+v
2
+v
4
+v
2
+v
3
+ v
4
+v
2
+v
4
+v
2
+ v
3
+v
3
+v
4
+v
1
+v
1
+ v
1
+ v
2
+v
3
+v
4
)


Page 67
P
`
A
1
(v
1
) =
1
24
(6v
1
+6v
2
+ 6v
3
+6v
4
) =
1
4
(v
1
+v
2
+v
3
+v
4
)
As you woulu pieuict this is the totally symmetiic stietch
A
1
stietching moue
Bo the same foi the T
2
moue
T
u
E 8C
S
SC
2
6S
4
6
u
T
2
S u -1 -1 1
P
`
1
2
(v
1
) =
S
24
(Sv
1
+u(v
1
+v
1
+v
2
+v
3
+v
3
+v
4
+v
2
+v
4
) v
2
v
3
v
4
v
2
v
4
v
2
v
3
v
3
v
4
+ v
1
+ v
1
+v
1
+v
2
+v
3
+v
4
)
P
`
1
2
(v
1
) =
S
24
(6v
1
2v
2
2v
3
2v
4
) =
1
4
(Sv
1
v
2
v
3
v
4
)
This is an asymmetiic stietching moue that is tiiply uegeneiate.
T
2
stietching moues
0ne must pioject out two othei basis functions to finu the othei two moues.
They will look iuentical but be iotateu ielative to the moue uiawn heie.
Notice the
1
function is uisplaceu S times moie than the othei S basis
functions.

Page 68
In an analogous mannei the benuing moues may be piojecteu to ieveal the
following:

E benuing moues T
2
benuing moues

Animations of these vibiations can be seen online heie:
http:www.molwave.comsoftwaieSunoimalmouesSunoimalmoues.htm


Page 69
Bonding Theories

Lewis Bonding Theory
Atoms seek to obtain an octet of elections in the outei shell (uuet foi
hyuiogen).
A single bonu is foimeu when two elections aie shaieu between two atoms
e.g. B:B
A uouble bonu is foimeu when two paiis of elections aie shaieu
e.g. 00
Lewis theoiy woiks well foi connectivity but uoes not give pieuictions about
thiee uimensional shape.

VSEPR Valence Shell Electron Pair Repulsion Theory
Pieuicts shape by assuming that atoms anu lone election paiis seek to
maximize the uistance between othei atoms anu lone paiis.
Woiks well foi shapes but must be combineu with Lewis theoiy foi
connectivity anu bonu oiuei.
e.g. An atom with foui things (i.e. bonus oi lone paiis) woulu auopt a
tetiaheuial geometiy with iespect to the things. The moleculai shape is
uesciibeu ielative to the bonus only.
NB
S
has thiee bonus anu one lone paii on the N atom, giving a tetiaheuial
geometiy. Bowevei, the shape of NB
S
is uesciibeu as tiigonal pyiamiual when
only the bonus aie consiueieu.


Page 7u
Valance Bond Theory
vB theoiy was uevelopeu in the 192us anu was the fiist quantum mechanical
uesciiption of bonuing. In vB theoiy bonus aie foimeu fiom the oveilap of
atomic oibitals between aujacent atoms. This theoiy pieuicteu uiffeient
shapes foi single () anu multiple () bonus.
Consiuei the oveilap of an election in hyuiogen 1s
1
oibital anu an election in
a caibon 2p
1
oibital

The iesulting oveilap of wavefunctions iesults in continuous election uensity
between the atoms which is classifieu as a bonuing inteiaction. The iesulting
bonu has cylinuiical symmetiy ielative to the bonu axis.

Bouble anu tiiple bonus foim fiom the oveilap of aujacent paiallel p-oibitals.
The iesult is shown below.

A uouble bonu consists of one bonu anu one bonu. A tiiple bonu is a
bonu anu two bonus.


Page 71
Hybrid Orbital Theory
vB theoiy gets us staiteu but we know that othei geometiies exist in
molecules. Consiuei caibon with a giounu state election configuiation of
|Be]2s
2
sp
2
. With the auuition of a small amount of eneigy one 2s election is
piomoteu to the 2p shell anu the following configuiation iesults
|Be]2s
1
2p
x
1
2p
y
1
2p
z
1
. This leaves foui half filleu oibitals that can oveilap with
othei oibitals on aujacent atoms.
Will this iesult in uiffeient types of bonus. 0veilap of an s-oibital anu a p-
oibital will not be the same. Bowevei, we know that in CB
4
all of the bonus
aie equivalent.
The solution is to cieate hybiiu oibitals that aie foimeu when we take lineai
combinations of the foui available atomic oibitals.
The foui unique lineai combinations that can be foimeu aie as follows
h
1
= s + p
x
+ p
y
+ p
z
h
2
= s p
x
p
y
+ p
z

h
S
= s p
x
+ p
y
p
z
h
4
= s + p
x
p
y
p
z

uiaphically the iesults aie shown below:


Page 72
These lineai combination give iise to foui new oibitals that have election
uensity pointeu along tetiaheuial angles. The oibitals aie nameu sp
S
hybiiu
oibitals.
0thei hybiiu oibitals aie possible with uiffeiing geometiy
0ibital Shape
sp Lineai
sp
2
Tiigonal planai
sp
S
Tetiaheuial
sp
S
u Tiigonal pyiamiual
sp
S
u
2
octaheuial

0veilap of the hybiiu oibitals with othei oibital (hybiiu oi atomic) uesciibe
the bonuing netwoik in molecule. Nultiple bonus aie foimeu with unuseu
p-oibitals oveilapping to foim bonus as uesciibeu in vB theoiy.
Molecular Orbital Theory
N0 theoiy was also uevelopeu uuiing the 192us anu is a quantum mechanical
uesciiption of bonuing. All of the pieceuing bonuing mouels aie teimeu
localizeu election bonuing mouels because it is assumeu that a bonu is foimeu
when elections aie shaieu between two atoms only. N0 theoiy allows foi
uelocalization of elections. That is, elections may be shaieu between moie
than two atoms ovei longei uistances.
Similaily to vB theoiy, N0s aie foimeu fiom the inteiaction of atomic
oibitals. Beie we foim lineai combinations of atomic oibitals. When we
combine two A0s we must foim two N0s
1
=
1s
A
+
1s
B

1
=
1s
A
1s
B


Page 7S

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 anti-bonuing.

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.

Quantum mechanical description of orbitals
Eiwin Schiouingei pioposeu a methou to finu election wavefunctions. The
time-inuepenuent Schiouingei equation in one uimension is
2
2m
J
2
Jx
2
+I(x) = E
wheie is the wavefunction anu

Page 74
=
2n
= 1.uS4 1u
-34

v(x) is the potential eneigy of the election at position x anu
anu
2
2m
d
2
dx
2
is the kinetic eneigy of the election. This equation is often
simplifieu as
= E
wheie
is calleu the Bamiltonian opeiatoi. Wiitten in this foim we see that

this is an Eigen value equation. The total eneigy of the election becomes the
Eigen value of the Bamiltonian anu is the Eigen function.
uesciibes the uynamic infoimation about a given election. The piobability
of finuing an election in a given volume of infinitely small size is
P = |
2
|J
J = JxJyJz
With iegaiu to specifically iuentifying the uynamic infoimation about an
election we aie limiteu by the following:
x p
1
2

This is known as the Beisenbeig unceitainty piinciple anu states that we
cannot know both the position anu momentum of a paiticle with aibitiaiy
piecision. x is the eiioi (unceitainty) in position anu p is the eiioi in
momentum.


Page 7S
Group Theory and Quantum Mechanics

If we exchange any two paiticles in a system by caiiying out a symmetiy
opeiation, the Bamiltonian must iemain unchangeu because we aie in an
equivalent state.
In othei woius, the Bamiltonian commutes with all R foi a gioup
R
R
Theie aie cases in which multiple Eigen functions give the same Eigen value.
1
= E
2
= E
2

:
n
= E
n

We say that the Eigen value is uegeneiate oi n-folu uegeneiate. In these cases
the Eigen functions aie a solution to the Schiouingei equation anu also any
lineai combination of the uegeneiate Eigen functions
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 non-uegeneiate Eigen function
we have
= E

so that R
i
is an Eigen function of the Bamiltonian.

Page 76
Because
i
is noimalizeu R
i
= _ 1
i
. Theiefoie if we apply all R in a gioup
to a non-uegeneiate
i
, we get a iepiesentation weie each matiix element,
i
(R) will be _ 1. A one-uimensional matiix is by uefinition iiieuucible.
A similai analysis foi n-folu 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
] _
(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.
Baitiee-Fock 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 (election-election
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.

Page 77

Hckel Orbital Method

We will use a ieuefineu Bamiltonian calleu the effective Bamiltonian.
E
c]],n
(p) =
coc
+{2[
(p) K
(p)]

wheie } anu K aie the Coulomb anu exchange integials iespectively. The
Coulomb integial takes into account the election-election 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.


Page 78

As it stanus so fai, we have a methou foi finuing the eneigies of N oibitals
foi N atoms. The iesult is an N-uimensional 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
-
)
O
N
O
-
O
N
O
-

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

Page 79
A0
S -1 1 -S

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
+
1
) =
1
2
(
1
3
)
P
I
B
1
(
2
) =
1
4
(
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
)

Page 8u
2
=
1
2
1
+
2
+
1
2
3
=
1
2
2
+
1
2
3

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)

Similaily we finu the noimalizeu
2
anu
S
to be
2
= _
2
3
[
1
2
1
+
2
+
1
2
3
(B
1
symmetiy)

Page 81
3
= _
2
3
[
1
2
1

2
+
1
2
3
(B
1
symmetiy)

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.


Page 82

Biawing pictuies of the oibitals helps to visualize the iesults

B
1
anti-bonuing oibital

o
4
S
[

A
2
non-bonuing oibital

o

B
1
bonuing oibital

o +
4
S
[


Page 8S
Nitiite oibitals calculateu using ab initio methous.
B
1
anti-bonuing oibital

A
2
non-bonuing oibital

B
1
bonuing oibital


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


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
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 two-uimensional, 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
3
+
4
)


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
4
) E symmetiy
4
=
1
2
(
1
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
.

Page 87
B
2u
anti-bonuing

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


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 non-unifoim
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.

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.


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 semi-empiiical 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
||


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
1
S
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
1
S
1
S
4
)
Now pioject the E oibitals
P
L
||
(
1
) =
1
12
(2
1
1
+2
1
1
) = u
Because
1
uoes not contiibute to the E oibital we must pioject two othei
basis functions anu take theii lineai combinations.

P
L
||
(
2
) =
2
12
(2
2
4
+2
2
4
) =
1
6
(2
2
4
)

Page 92
P
L
||
(
3
) =
2
12
(2
3
2
+2
3
2
) =
1
6
(2
3
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


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 top-uown view. The sign of the wavefunction is opposite
on the bottom siue.


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


Page 9S
Homework Set 4 Final Exam
Take home final. You may use youi book anu class notes but please woik on
youi own. Exams aie uue Fiiuay befoie noon. Tuin them in to my chemistiy
uepaitment mailbox. You must cleaily show all of youi woik foi full cieuit.

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.

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


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

Group Theory - Lecture Notes

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Couise Lectuie Notes

Intiouuction to the Chemical Applications of uioup Theoiy

foi n-uimensional space

= complex conjugate of the element in the m

. Bowevei, in this case we see by inspection that

will be uiscusseu latei.

is the iauius vectoi foi a nucleus

= the uimension of the iiieuucible iepiesentation

(R)= chaiactei of opeiation R

is calleu the Bamiltonian opeiatoi. Wiitten in this foim we see that

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