SIMETRI S1 Kimia

Symmetry and Group Theory
Feature: Application for Spectroscopy

and Orbital Molecules
Page 1
Text books
P. H. Walton Beginning Group Theory for Chemistry
Oxford University Press Inc., New York, 1998
ISBN 019855964
A.F.Cotton Chemical Applications of Group Theory
ISBN 0471510947
Page 2
Unsur simetri dan operasi simetri molekul

Operasi simetri
Suatu operasi yang dikenakan pada suatu molekul
sedemikian rupa sehingga mempunyai orientasi
baru yang seolah-olah tak terbedakan dengan
orientasi awalnya
Unsur simetri
Suatu titik, garis atau bidang sebagai basis
operasi simetri
Page 3
Simbol
Unsur
Operasi
Unsur identitas
Membiarkan obyek tidak

berubah
Cn
Sumbu rotasi
Rotasi seputar sumbu dengan

derajat rotasi 360/n (n adalah
bilangan bulat)
Bidang simetri
Refleksi melalui bidang simetri
Pusat/titik inversi
Proyeksi melewati pusat

inversi ke sisi seberangnya
dengan jarak yang sama dari
pusat
Sn
Sumbu rotasi tidak

sejati (Improper
rotational axis)
Rotasi mengitari sumbu rotasi

diikuti dengan refleksi pada
bidang tegak lurus sumbu
rotasi
Page 4
Operasi Simetri
Imperial College London
Rotations 360/n where n is an integer
BF3
Operation rotation by 360/3
around C3 axis (element)
F3
F2
Rotate 120O
B
F2
Page 6
B
F1
F1
F3
Reflections
Reflection is the operation
element is plane of symmetry
x is out of the plane
y
H2O
x
(xz)
H2
Page 7
H1
H1
H2
H2
H1
(yz)
Reflections for H2O

Page 8
Reflections
Principle (highest order) axis is defined as Z axis
After Mulliken
(xz) in plane perpendicular to molecular plane
(yz) in plane parallel to molecular plane
both examples of v
v : reflection in plane containing highest order axis
h : reflection in plane perpendicular to highest
order axis
d : dihedral plane generally bisecting v
Page 9
XeF4
Reflections v
F
Xe
Xe
F
d
F
Xe
Page 10
XeF4
Page 11
Examples: Benzene, XeF4

Ethene
Inversion
i element is a centre of symmetry

Atom at (-x,-y,-z)
Atom at (x,y,z)
Z
Y
X
Page 12
Inversion , i
Centre of inversion
Y
X
H
C
H
S4 Improper Rotation
Rotate about C4 axis and then reflect
perpendicular to this axis
S4
C4
Page 13
S4 Improper Rotation
Page 14
successive operation
Page 15
TEORI GRUP
Page 16
Mathematical Definition: Group Theory
A group is a collection of elements having certain properties

that enables a wide variety of algebraic manipulations to be
carried out on the collection
Because of the symmetry of molecules they can
be assigned to a point group
Page 17
Steps to classify a molecule into a point group

Question 1:
Is the molecule one of the following recognisable
groups ?
NO: Go to the Question 2
YES: Octahedral point group symbol Oh
Tetrahedral point group symbol Td
Linear having no i C
Linear having i Dh
Page 18

Question 1:
Is the molecule one of the following recognisable
groups ?
NO: Go to the Question 2
YES: Octahedral point group symbol Oh
Tetrahedral point group symbol Td
Linear having no i C
Linear having i Dh
Page 19

Question 2:
Does the molecule possess a rotation axis of order 2 ?
YES: Go to the Question 3
NO:
If no other symmetry elements point group symbol C1
If having one reflection plane point group symbol Cs
If having i Ci
Page 20

Question 3:
Has the molecule more than one rotation axis ?
YES: Go to the Question 4

NO:
If no other symmetry elements point group symbol Cn (n is the order of
the principle axis)
If having n h point group symbol Cnh
If having n v Cnv
If having an S2n axis coaxial with principal axis S2n
Page 21

Question 4:
The molecule can be assigned a point group as
follows:
No other symmetry elements present Dn
Having n d bisecting the C2 axes Dnd
Having one h Dnh
Page 22
Molecule
Linear?
Dh
i?
2 or more
Cn, n>2?
Cv
i?
Ih
C5?
Oh
Td
*
Dnh
Dnd
Page 23
h?
nd?
Cn?
N
Dn
Cs
Cnh
h?
Cnv
nv?
S2n
S2n?
Ci
Cn
i?
Select Cn with highest n,

nC2 perpendicular to Cn?
C1
Benzene
Linear?
Dh
i?
2 or more
Cn, n>2?
Cv
i?
Ih
Benzene
is D6h
Oh
Td
*
Dnh
Dnd
Page 24
C5?
h?
nd?
Cn?
n=6
N
Dn
Cs
Cnh
h?
Cnv
nv?
S2n
S2n?
Ci
Cn
i?
Select Cn with highest n,

nC2 perpendicular to Cn?
C1
Tugas I: Symmetry and Point Groups

Tentukan unsur simetri dan grup titik pada
molekul
a. N2F2
b. POCl3
Gambarkan geometri masing-masing
molekul tersebut
Page 25
KULIAH MINGGU III
Page 26
Basic Properties of Groups
Any Combination of 2 or more elements of the collection must be

equivalent to one element which is also a member of the collection
AB = C
where A, B and C are all members of the collection
There must be an IDENTITY ELEMENT (E)
AE = A
for all members of the collection
E commutes with all other members of the group
AE= EA =A
Page 27
The combination of elements in the group must be ASSOCIATIVE

A(BC) = AB(C) = ABC
Multiplication need not be commutative
(ie: ACCA)
Every member of the group must have an INVERSE which is also a
member of the group.
AA-1 = E
Example of Group Properties
H
B(OH)3 belongs to C3 point group
B
O
O
H
Page 28
It has E, C3 and C32

symmetry operations
Any Combination of 2 or more elements of the collection must be equivalent to

one element which is also a member of the collection
AB = C
where A, B and C are all members of the collection
H2
O
H1
C3
B
O
H3
H1
O
H3
H3
B
O
H2
2
H2
Overall: C3 followed C3 gives C32

Page 29
C3
B
O
O
H1
There must be an IDENTITY ELEMENT (E)

AE = A
for all members of the collection
E commutes with all other members of the group
H2
O
H1
H3
C32
B
O
AE= EA =A
O
H3
H2
3
H1
B
O
C32
H3
1
H1
E. C32 = C32 and C32. C3 = E and C32. C32 = C3

Page 30
B
O
O
H2
The combination of elements in the group must be ASSOCIATIVE

A(BC) = AB(C) = ABC
Multiplication need not be commutative
(ie: ACCA)
C3 .(C3 .C32 )= (C3 .C3) C32

(Do RHS First)
C3.C32 = E ;
C3 .E = C3
C3 .C3 = C32 ;
C32 .C32 = C3
Operations are associative and E, C3 and C32 form a group
Page 31
Group Multiplication Table

Order of the group =3
C3
C3
C32
Every member of the group must
C3
C32
have an INVERSE which is also

a member of the group.
C3
C3
C32
C32
C32
C3
AA-1 = E
The inverse of C32 is C3

The inverse of C3 is C32
Page 32
KULIAH MINGGU IV-V
Page 33
Math Based
Matrix math is an integral
part of Group Theory;
however, we will focus on
application of the results.
For multiplication:
Number of vertical columns in the
first matrix = number of horisontal
rows of the second matrix
Product:
Row is determined by the row of
the first matrix and columns by the
column of the second matrix
34
Math based
[1 2 3]
1
0
0
0
-1
0
0
0
1
35
Representations of Groups
Diagrams are cumbersome

Require numerical method
Allows mathematical analysis
Represent by VECTORS or Mathematical Functions
Attach Cartesian vectors to molecule
Observe the effect of symmetry operations on these vectors
Vectors are said to form the basis of the representation each

symmetry operation is expressed as a transformation matrix
[New coordinates] = [matrix transformation] x [old coordinates]
Page 36
Constructing the Representation

Put unit vectors on each atom
z
S
O
x
C2v: [E, C2, xz, yz]
These are useful to describe molecular vibrations
and electronic transitions.
Page 37

A unit vector on each atom represents translation in the y direction
C2
S
O
Page 38
S
O
C2.(Ty) = (-1) Ty
E .(Ty) = (+1) Ty
yz .(Ty) = (+1) Ty
xz .(Ty) = (-1) Ty

A unit vector on each atom represents rotation around the z(C 2) axis
S
O
Page 39
O
C2.(Rz) = (+1) Rz
E .(RZ) = (+1) Rz
yz .(Rz) = (-1) Rz
xz .(RZ) = (-1) RZ
C2v
Page 40
C2
(xz)
(yz)
+1
+1
+1
+1
Tz
+1
+1
-1
-1
Rz
+1
-1
+1
-1
Tx,Ry
+1
-1
-1
+1
Ty,Rx

Use a mathematical function
Eg: py orbital on S
S
O
C2v
Page 41
O
E
C2
(xz)
(yz)
+1
-1
-1
+1
Ty,Rx
py has the same symmetry properties as Ty and Rx vectors
h
Au
[AuCl4]-
C4
Au
C.[d x2-y2] =
(-1) .[d x2-y2]
Page 42
Au
h.[d x2-y2] =
(+1) .[d x2-y2]
Effects of symmetry operations generate the

TRANSFORM MATRIX
Simple examples so far.
For all the symmetry operations of D4h on [d x2-y2]
We have:
D4h
Page 43
2C4
C2
2C2 2C2 I
2S4
2v
2d
+1
-1
+1
+1
-1
+1
+1
-1
-1
+1
Constructing the Representation:

The TRANSFORMATION MATRIX
Examples can be more complex:
e.g. the px and py orbitals in a system with a C4 axes.
Y
C4
X
In matrix form:
Page 44
p x ' 0 1 p x
p '
p
1
0
y
y
px
px py
py
py px
A 2x2 transformation
matrix

Vectors and mathematical functions can be used to build a
representation of point groups.
There is no limit to the choice of these.
Only a few have fundamental significance. These cannot be
reduced.
The IRREDUCIBLE REPRESENTATIONS
Any REDUCIBLE representation is the SUM of the set of
IRREDUCIBLE representations.
Page 45

If a matrix belongs to a reducible representation it can be transformed
so that zero elements are distributed about the diagonal
a11
a
21
a 31
a12
a 22
a 32
a13
a 23
a 33
Similarity Transformation
A goes to B
The similarity transformation is such that

C-1 AC = B where C-1C=E
Page 46
b11 b21 0
b
b
0
21 22
0
0 b33

Generally a reducible representation A can be reduced such
That each element Bi is a matrix belonging to an irreducible representation .
All elements outside the Bi blocks are zero
B1
This can generate very large matrices.

However, all information is held in the character of these matrices
Page 47
..
..
B2
Bn
Character Tables
a11
a
21
a 31
a12
a 22
a 32
a13
a 23
a 33
Character , = a11 + a22 + a33.
In general
a nm
i 1
And only the character , which is a number is required and

NOT the whole matrix.
Page 48
Character Tables an Example C3v : (NF3)
C3v
C 31 C 32 v v v
-1 -1 -1
Rz
-1
-1
(Tx,Ty) or (Rx,Ry)
1
0
1
0
Tz
This simplifies further. Some operations are of the same class and always have the
same character in a given irreducible representation
Page 49
C31, C31
are in the same class
v, v, v
are in the same class
Character Tables an Example C3v : (NF3)
C3v
2C3 v
A1
Tz
A2
-1
Rz
-1
(Tx,Ty) or (Rx,Ry)
x2 + y2
(x2, y2, xy) (yz, zx)
There is a nomenclature for irreducible representations: Mulliken Symbols

A is single and E is doubly degenerate (ie x and y are indistinguishable)
Page 50
Note:
You will not be asked to generate character tables.
These can be brought/supplied in the examination
Page 51
KULIAH MINGGU VI-VII-VIII
Page 52
General form of Character Tables:

(a)
(b)
(f)
(c)
(d) (e)
(a) Gives the Schonflies symbol for the point group.

(b) Lists the symmetry operations (by class) for that group.
(c) Lists the characters, for all irreducible representations for each class
of operation.
(d) Shows the irreducible representation for which the six vectors
Tx, Ty, Tz, and Rx, Ry, Rz, provide the basis.
(e) Shows how functions that are binary combinations of x,y,z (xy or z2)
provide bases for certain irreducible representation.(Raman d orbitals)
(f)Page
List
conventional symbols for irreducible representations:
53
Mulliken symbols
Mulliken symbols: Labelling

All one dimensional irreducible representations are labelled A or B.
All two dimensional irreducible representations are labelled E.

(Not to be confused with Identity element)
All three dimensional representations are labelled T.

For linear point groups one dimensional representations are
given the symbol with two and three dimensional representations
beingand
Page 54

1)
A one dimensional irreducible representation is labelled A if it is symmetric

with respect to rotation about the highest order axis C n.
(Symmetric means that = + 1 for the operation.)
If it is anti-symmetric with respect to the operation = - 1 and it is labelled B.
2)
A subscript 1 is given if the irreducible representation is symmetric with respect
to rotation about a C2 axis perpendicular to Cn or (in the absence of such an axis)
to reflection in a vplane. An anti-symmetric representation is given the subscript 2.
For linear point groups symmetry with respect to s is indicated by a superscript
+ (symmetric) or (anti-symmetric)
Page 55

3)
Subscripts g (gerade) and u (ungerade) are given to irreducible representations
That are symmetric and anti-symmetric respectively, with respect to inversion
at a centre of symmetry.
4)
Superscripts and are given to irreducible representations that are symmetric
and anti-symmetric respectively with respect o reflection in a h plane.
Note: Points 1) and 2) apply to one-dimensional representations only.
Points 3) and 4) apply equally to one-, two-, and three- dimensional representations.
Page 56
Generating Reducible Representations

zs
z1
O
x1
S ys
xs
x2
Page 57
For the symmetry operation
x1 x2
O
y1
xz
z2
xz (a v )
x2 x1 xs xs
y2
y1 -y2 y2 -y1 ys -ys
z1 z2
z2 z1
zs zs

In matrix form
x1 0 0
y 0 0
1
z1 0 0

x2 1 0
( xz ) y2 0 1

z2 0 0
x 0 0
s
yy 0 0
z 0 0
s
Page 58
0
0
0
0
1 0
0 1
0 0
0 0
0
0
1
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0 0
0 0
1 0
0 1
0 0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
x1 x2
y y
2
1
z1 z2

x2 x1
. y2 y1

z 2 z1
x x
s s
ys ys
z z
s s
x1 0 0
y 0 0
1
z1 0 0

x2 1 0
( xz ) y2 0 1

z2 0 0
x 0 0
s
yy 0 0
z 0 0
s
0
0
0
0
0
1
0
0
0
1 0
0 1
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0
0
1
0
0
0
0
0
0
0 0
0 0
0 0
0 0
0 0
0 0
1 0
0 1
0 0
0
0
0
0
0
0
0
0
1
x1 x2
y y
2
1
z1 z 2

x
x
2 1
. y2 y1

z 2 z1
x x
s s
ys ys
z z
s s
Only require the characters: The sum of diagonal elements

For (xz) = + 1
Page 59
x1 1
y 0
1
z1 0

x2 0
( yz ) y2 0

z2 0
x 0
s
yy 0
z 0
s
0
1
0
0
0
0
0
0
0
0 0
0 0
1 0
0 1
0 0
0 0
0 0
0 0
0 0
0
0
0
0
1
0
0
0
0
0 0
0 0
0 0
0 0
0 0
1 0
0 1
0 0
0 0
For (yz) = + 3
Page 60
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
1
x1 x1
y y
1 1
z1 z1

x
2
2
. y2 y2

z2 z2
x x
s
s
ys ys
z z
s s
x1
y
1
z1

x2
E y2

z2
x
s
yy
z
s
1 0 0 0 0 0 0 0 0
0 1 0 0 0 0 0 0 0
0 0 1 0 0 0 0 0 0
0
0
0
1
0
0
0
0
0
0 0 0 0 1 0 0 0 0
0 0 0 0 0 1 0 0 0
0 0 0 0 0 0 1 0 0
0 0 0 0 0 0 0 1 0
0 0 0 0 0 0 0 0 1
For E = + 9
Page 61
x1 x1
y y
1 1
z1 z1

x 2 x2
. y2 y2

z2 z2
x x
s s
ys ys
z z
s s
x1
y
1
z1
0 1
0
0
0
0
0
0
1 0
0 1

x
2
C2 . y2

z2
x
s
yy
z
s
1 0 0
0 1 0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
For C2 = -1
Page 62
0
0 0 0
0 0 0

0 0 0
0 0 0 .

0 0 0
1 0 0

0 1 0
0 0 1
0
x2
y
2
x1
y1
z1

x2
y2

z2
xs

ys
z s
z2
x1
y1
z1
xs
ys
z s

Summarising we get that 3n for this molecule is:
C2v
C2
(xz)
(yz)
3n
+9
-1
+1
To reduce this we need the character table for the point groups
Page 63
C2v
C2
(xz)
(yz)
A1
+1
+1
+1
+1
Tz
x2, y2, z2
A2
+1
+1
-1
-1
Rz
xy
B1
+1
-1
+1
-1
Tx , Rx
xz
B2
+1
-1
-1
+1
Ty , Ry
yz
Reducing Reducible Representations
We need to use the reduction formula:
1
a p
g
. ( R). p R
Where ap is the number of times the irreducible representation, p,

occurs in any reducible representation.
g is the number of symmetry operations in the group

(R) is character of the reducible representation
p(R) is character of the irreducible representation
nR is the number of operations in the class
Page 64
C2v 1E
1C2
(xz)
(yz)
A1
+1
+1
+1
+1
Tz
x2, y2, z2
A2
+1
+1
-1
-1
Rz
xy
B1
+1
-1
+1
-1
Tx , Rx
xz
B2
+1
-1
-1
+1
Ty , Ry
yz
C2v
C2
(xz)
(yz)
3n
+9
-1
+1
For C2v ; g = 4 and nR = 1 for all operations
Page 65
1
a p
g
n
R
. ( R). p R
C2v
C2
(xz)
(yz)
3n
+9
-1
+1
aA1 = (1/4)[ ( 1x9x1) + (1x-1x1) + (1x1x1) + (1x3x1)] = (12/4) =3

aA2 = (1/4)[ ( 1x9x1) + (1x-1x1) + (1x1x-1) + (1x3x-1)] = (4/4) =1
aB1 = (1/4)[ ( 1x9x1) + (1x-1x-1) + (1x1x1) + (1x3x-1)] = (8/4) =2
aB2 = (1/4)[ ( 1x9x1) + (1x-1x-1) + (1x1x-1) + (1x3x1)] = (12/4) =3
3n = 3A1 + A2 + 2B1 + 3B2
Page 66
Reducing Reducible Representations

aA1 = (1/4)[ ( 1x9x1) + (1x-1x1) + (1x1x1) + (1x3x1)] = (12/4) =3
The terms in blue represent contributions from the un-shifted atoms
Only these actually contribute to the trace.
If we concentrate only on these un-shifted atoms we can
simplify the problem greatly.
For SO2 (9 = 3 x 3) ( -1 = 1 x 1) (1 = 1 x 1) and ( 3 = 3 x 1)
Number of un-shifted atoms
Page 67
Contribution from these atoms
Identity E
z
z1
E
y
x
For each un-shifted atom
Page 68
x1 1 0 0
y 0 1 0
1
z1 0 0 1
x
y
z
y1
x1
(E) = +3
Inversion i
x1
z
y1
i
y
z1
x
x1 1 0 0
y 0 1 0
1
z1 0 0 1
Page 69
x
y
z
(i) = -3
Reflection (xz)
(Others are same except location of 1 changes)

z1
z
(xz)
y
x
x1 1 0 0 x
y 0 1 0 . y
1

z1 0 0 1 z
Page 70
y1
x1
((xz)) = +1
Rotation Cn
z1
z
Cn
y
x1
x
360/n
x1
y
1
z1
360
cos
360
sin
n
0
Page 71
360
360
cos
n
0
sin
y1

0 .
x
y
z
(Cn) = 1 + 2.cos(360/n)
Improper rotation axis, Sn
(xy)
Cn
y
x1
y1
360
cos
n
360
sin
x1
y
1
z1
Page 72
360
n
360
cos
sin

0 .
x
y
z
z1
(Sn) = -1 + 2.cos(360/n)
Summary of contributions from un-shifted atoms to 3n
Page 73
(R)
+3
-3
1+ 2.cos(360/n) C2
+1
1+ 2.cos(360/n) C3 ,C32
1+ 2.cos(360/n) C4, C43
+1
-1 + 2.cos(360/n) S31,S32
-2
-1 + 2.cos(360/n) S41,S42
-1
-1 + 2.cos(360/n) S61,S65
-1
Worked example: POCl3 (C3v point group)

(R)
R
E
v
C3
C l
2C3
A1
A2
E
1
2
1
-1
-1
0
Un-shifted
atoms
Contribution
3
15
0
0
1
3
Page 74
3n
C l
+3
+1
0
E
C3v
C l
Number of classes,
(1 + 2 + 3 = 6)
Order of the group,
g=6
Reducing the irreducible representation for POCl3
1
a p
g
. ( R). p R
C3v
3n
2C3
15
a(A1) =
1/6[(1x 15x1) + (2 x 0 x 1) + (3 x 3x 1)] = 1/6 [15 + 0+ 9] = 4
a(A2) =
1/6[(1 x 15 x 1) + ( 2 x 0 x 1) + (3 x 3x 1)] = 1/6 [15 + 0 -9] = 1
a(E) =
1/6[ (1 x 15 x 2) + (2 x 0 x 1) + (3 x 3 x 0)] = 1/6[30 + 0 + 0 ] =5
3n = 4A1 + A2 + 5E
For POCl3 n= 5 therefore the number of degrees of freedom is 3n =15.
E is doubly degenerate so 3n has 15 degrees of freedom.
Page 75
KULIAH MINGGU IX-X-XI-XII

APLIKASI TEORI GRUP
Page 76
Group Theory and Vibrational Spectroscopy: SO2

C2v 1E
1C2
(xz)
(yz)
A1
+1
+1
+1
+1
Tz
x2, y2, z2
A2
+1
+1
-1
-1
Rz
xy
B1
+1
-1
+1
-1
Tx , Rx
xz
B2
+1
-1
-1
+1
Ty , Ry
yz
C2v
C2
(xz)
(yz)
3n
+9
-1
+1
3n = 3A1 + A2 + 2B1 + 3B2

Page 77
Group Theory and Vibrational Spectroscopy: SO2

3n = 3A1 + A2 + 2B1 + 3B2 = 3 + 1 + 2 + 3 = 9 = 3n
For non linear molecule there are 3n-6 vibrational degrees of freedom
C2v 1E
1C2
(xz)
(yz)
A1
+1
+1
+1
+1
Tz
x2, y2, z2
A2
+1
+1
-1
-1
Rz
xy
B1
+1
-1
+1
-1
Tx , Rx
xz
B2
+1
Ty , Ry
yz
-1
-1
+1
vib = 3n rot trans
3n = 3A1 + A2 + 2B1 + 3B2

rot =
A2 + B1 + B2
trans = A1
+ B1 + B2
vib = 2A1 + B2
Page 78
(Degrees of freedom = 2 + 1 = 3 = 3n-6)
Group Theory and Vibrational Spectroscopy: POCl3

3n
= 4A1 + A2 + 5E
trans = A1
rot =
vibe = 3A1
+ E
A2 + E
C l
C l
There are nine vibrational modes . (3n-6 = 9)

The E modes are doubly degenerate and
constitute TWO modes
+ 3E
There are 9 modes that transform as 3A1 + 3E.

These modes are linear combinations of the three vectors
attached to each atom.
Each mode forms a BASIS for an IRREDUCIBLE representation
of the point group of the molecule
Page 79
C l
From 3n to vibe and Spectroscopy

Now that we have vibe what does it mean?
We have the symmetries of the normal modes of vibrations.
In terms of linear combinations of Cartesian co-ordinates.
We have the number and degeneracies of the normal modes.
Can we predict the infrared and Raman spectra?
Yes!!
Page 80
Applications in spectroscopy: Infrared Spectroscopy

Vibrational transition is infrared active because of interaction
of radiation with the:
molecular dipole moment, .
There must be a change in this dipole moment
This is the transition dipole moment
Probability is related to transition moment integral .
Page 81
Infrared Spectroscopy
TM i* f d i f d
Is the transition dipole moment operator and

has components: x, y, z.
Note: Initial wavefunction

is always real
Page 82
f
i
Wavefunction final state

Wavefunction initial state
Infrared Spectroscopy
Transition is forbidden if TM = 0
Only non zero if direct product:
f i
contains the totally symmetric representation.
IE all numbers for in representation are +1
The ground state i is always totally symmetric
Dipole moment transforms as Tx, Ty and Tz.
The excited state transforms the same as the vectors that describe
the vibrational mode.
Page 83
The DIRECT PRODUCT representation.

TM i* f d i f d
T x
i T y f
T
z
For SO2 we have that:
vib = 2A1 + B2
Under C2v :
Tx, Ty and Tz transform as B1, B2 and A1 respectively.
Page 84
Page 85
C2
(xz) (yz)
C2V
A1
+1 +1
+1
+1
A2
+1 +1
Rz
B1
+1 1
+1
x, Ry
B2
+1 1
+1
y, Rx
A1 B 1 A 1
+1 1
+1
B1
A1 B 2 A 1
+1 1
+1
B2
A 1 A 1 A1
+1 +1
+1
+1
A1
A1 B 1 B 2
+1 +1
A2
A1 B 2 B 2
+1 +1
+1
+1
A1
A1 A 1 B 2
+1 1
+1
B2
The DIRECT PRODUCT representation

Group theory predicts only A1 and B2 modes
B1
B1
A1 B2 A1 B2
A
A
1
1
B1
A2
A1 B2 B2 A1
A
B
1
2
Both of these direct product representations contain

the totally symmetric species so they are symmetry allowed.
This does not tell us the intensity only whether they are allowed
or not.
vib = 2A1 + B2
Page 86
We predict three bands in

the infrared spectrum of SO2
Infrared Spectroscopy : General Rule

If a vibrational mode has the same symmetry properties
as one or more translational vectors(Tx,Ty, or Tz) for that
point group, then the totally symmetric representation is
present and that transitions will be symmetry allowed.
Note:
Selection rule tells us that the dipole changes during a vibration
and can therefore interact with electromagnetic radiation.
Page 87
Raman Spectroscopy
Raman effect depends on change in polarisability .

Measures how easily electron cloud can be distorted
How easy it is to induce a dipole
Intermediate is a virtual state
THIS IS NOT AN ABSORPTION
Usually driven by a laser at 1.
Scattered light at 2.
Can be Stokes(lower energy) or Anti-Stokes shifted
Much weaker effect than direct absorption.
Page 88
Raman Spectroscopy
Virtual state
Stokes Shifted
Page 89
f
i

Wavefunction initial state
Raman Spectroscopy
Anti-Stokes Shifted
Page 90
Virtual state
Wavefunction intial state
Raman Spectroscopy
Probability of a Raman transistion:
i
f d
The operator , , is the polarisability tensor
xx
yx

zx
xy xz
yy yz
zy zz
For vibrational transitions ij = ji

so there are six distinct components:
x2, y2, z2, xy, xz and yz
Page 91
Raman Spectroscopy
For C2v
x2, y2, z2, xy, xz and yz
Transform as:
A1, A1, A1, A2, B1 and B2
We can then evaluate the direct product representation
in a broadly analagous way
Page 92
Raman Spectroscopy The DIRECT PRODUCT representation

For SO2 group theory predicts only A1 and B2 modes
A1
A2
A`1
A1
A2
A1
B1
B1
B
B
2
2
A1
A2
A`1
B2
B1
B2
B1
A2
B
A
2
1
Both of these direct product representations contain

the totally symmetric species so they are symmetry allowed.
We predict three bands in the Raman spectrum of SO2
Page 93
Note: A1 modes are polarised
Raman Spectroscopy : General Rule

If a vibrational mode has the same symmetry as on or more
Of the binary combinations of x,y and z the a transition from
this mode will be Raman active.
Any Raman active A1 modes are polarised.
Infrared and Raman are based on two DIFFERENT phenomena
and therefore there is no necessary relationship
between the two activities.
The higher the molecular symmetry the fewer co-incidences
between Raman and infrared active modes.
Page 94
Analysis of Vibrational Modes:

Vibrations can be classified into Stretches, Bends and Deformations
For SO2 vib = 2A1 + B2
We could choose more natural co-ordinates
z
r1
y
x
Page 95
r2
Determine the representation for stretch
r1
How does our new basis transform

Under the operations of the group?
r2
Vectors shifted to new position contribute zero

Unshifted vectors contribute + 1 to (R)
C2v
stre
C2
(xz)
+2
(yz)
+2
This can be reduced using reduction formula or by inspection:

( 1, 1, 1, 1)(A1) + (1,-1, -1, 1) (B2) = (2, 0, 0, 2)
stre = A1 + B2
Page 96

Two stretching vibrations exist that transform as A1 and B2.
These are linear combinations of the two vectors along the bonds.
We can determine what these look like by using symmetry adapted
linear combinations (SALCs) of the two stretching vectors.
Our intuition tells us that we might have a symmetric and an
anti-symmetric stretching vibration
A1 and B2
Page 97
Symmetry Adapted Linear Combinations
r1
Pick a generating vector eg: r1
r2
How does this transform under symmetry operations?

C2v
C2
(xz)
(yz)
r1
r1
r2
r2
r1
Multiply this by the characters of A1 and B2

For A1 this gives:
(+1) r1+ (+1) r2 + (+1) r2 + (+1) r1 = 2r1 + 2r2
Normalise coefficients and divide by sum of squares:
Page 98
1
2
(r1 r2 )
Symmetry Adapted Linear Combinations

For B2 this gives:
(+1) r1+ (-1) r2 + (-1) r2 + (+1) r1 = 2r1 - 2r2
Normalise coefficients and divide by sum of squares:
(r1 r2 )
2
S
O
A1
B2
Sulphur must also move to maintain position of centre of mass

Page 99
S
Remaining mode likely to be a bend
C2v
C2
(xz)
bend
(yz)
1
By inspection this bend is A1 symmetry

SO2 has three normal modes:
A1 stretch:
A1 bend:
B2 stretch:
Page 100
Raman polarised and infrared active

Raman polarised and infrared active
Raman and infrared active
Page 101
SO2 experimental data.
IR(Vapour)/cm-1
Raman(liquid)/cm-1
Sym
Name
518
524
A1 bend
1151
1145
A1 stretch
1362
1336
B2 stretch
SO2 experimental data.
Notes:
Stretching modes usually higher in frequency than bending modes
Differences in frequency between IR and Raman are due to
differing phases of measurements
Normal to number the modes According to how the Mulliken term
symbols appear in the character table, ie. A1 first and then B2
Page 102
Analysis of Vibrational Modes: POCl3
C l
C l
C l
C l
C l
C l
C l
C l
Angle deformations
P-Cl stretch
P=O stretch
vibe = 3A1 + 3E
3 A1 vibrations IR active(Tz) + Raman active polarised( x2 + y2 and z2)

3 E vibrations IR active(Tx,Ty) + Raman active ( x2 - y2 , xy) (yz,zx)
Page 103
C l
Six bands, Six co-incidences

C3v
E 2C3
3v
P=O str
P-Cl str
bend
vibe = 3A1 + 3E
Using reduction formulae or by inspection:

P=O str = A1 and P-Cl str = A1 + E
bend = vibe - P=O str - P-Cl str = 3A1 + 3E 2A1 E = A1 + 2E
Reduction of the representation for bends gives: bend = 2A1 + 2E
Page 104

bend = vibe - P=O str - P-Cl str = 3A1 + 3E 2A1 E = A1 + 2E
Reduction of the representation for bends gives: bend = 2A1 + 2E
One of the A1 terms is REDUNDANT as not
all the angles can symmetrically increase
bend = A1 + 2E
Note:
It is advisable to look out for redundant co-ordinates and think
about the physical significance of what you are representing.
Redundant co-ordinates can be quite common and can lead to a
double counting for vibrations.
Page 105

IR (liq)/ cm-1 Raman /cm-1 Description
Sym
Label
1292
1290(pol)
P=O str( 1,4)
A1
580
582
P-Cl str(2,3)
487
486(pol)
P-Cl str( 1,2,3)
A1
340
337
deformation
267
267(pol)
Sym.
Deformation(1)
A1
193
deformation
Page 106

1) All polarised bands are Raman A1 modes.
2) Highest frequencies probably stretches.
3) P-Cl stretches probably of similar frequency.
4)Double bonds have higher frequency than similar single bonds.
A1 modes first. P=O highest frequency
Then P-Cl stretch, then deformation.
581 similar to P-Cl stretch so assym. stretch.
Remaining modes must therefore be deformations
Could now use SALCs to look more closely at the normal modes
Page 107
Symmetry, Bonding and Electronic Spectroscopy
Page 108
Use atomic orbitals as basis set.

Determine irreducible representations.
Construct QULATITATIVE molecular orbital diagram.
Calculate symmetry of electronic states.
Determine allowedness of electronic transitions.

bonding in AXn molecules e.g. : water
How do 2s and 2p orbitals transform?
O 2s orbital
E, C2, xz, yx
O
H
Page 109
O
H
C2V
C2
xz
yz
O2s
a1

s-orbitals are spherically symmetric and when at the
most symmetric point always transform as the totally
symmetric species
For electronic orbitals, either atomic or molecular,
use lower case characters for Mulliken symbols
Oxygen 2s orbital has a1 symmetry in the C2v point group
Page 110

How do the 2p orbitals transform?
O 2pz orbital
E, C2, xz, yx
O
H
Page 111
C2V
C2
xz
yz
O2pz
a1

How do the 2p orbitals transform?
E, yx
O 2py orbital
C2, xz
Page 112
C2V
C2
xz
yz
O2py
b2
O2px
b1

How do the 2s and 2p orbitals transform?
Oxygen 2s and 2pz transforms as a1
2px transforms as b1 and 2py as b2
Need a set of -ligand orbitals of correct symmetry to interact
with Oxygen orbitals.
Construct a basis, determine the reducible representation,
reduce by inspection or using the reduction formula, estimate overlap,
draw MO diagram
Page 113

Use the 1s orbitals on the hydrogen atoms
z
H 1s orbitals
O
H
+
H+
Page 114
C2V
C2
xz
yz
a 1 + b2

Assume oxygen 2s orbitals are non bonding
Oxygen 2pz is a1, px is b1 and py is b2
Ligand orbitals are a1 and b2
Orbitals of like symmetry can interact
Oxygen 2px is wrong symmetry therefore likely to be non-bonding
Which is lower in energy a1 or b2?
Guess that it is a1 similar symmetry better interaction?
Page 115
Qualitative MO diagram for H2O

a1*
b2*
non-bonding (O 2px)
b1
a1 + b1 + b2
a1 + b2
b2
a1
a1
a1
non-bonding
2s
O
Page 116
H2O
2H

Is symmetry sufficient to determine ordering of a1 and b2 orbitals?
Construct SALC and asses degree of overlap.
Take one basis that maps onto each other
Use or as a generating function.
(These functions must be orthogonal to each other)
Observe the effect of each symmetry operation on the function
Multiply this row by each irreducible representation of the point
Group and then normalise.
(Here the irreducible representation is already known)
Page 117
C2V
C2
xz
yz
a1
Sum and normalise
b2
Sum and normalise
pz
b2 = 1/2(1 2)
H+
Page 118
a1 = 1/2(1 + 2)
(a1)
(b2)
py

The overlap between the a1 orbitals ( is greater than
that for the b2 orbitals (
Therefore a1 is lower in energy than b1.
We can use the Pauli exclusion principle and the Aufbau principle
To fill up these molecular orbitals.
This enables us to determine the symmetries of electronic states
arising from each electronic configuration.
Note: Electronic states and configurations are NOT the same thing!
Page 119
Qualitative MO diagram for H2O

a1*
b2*
non-bonding (O 2px)
b1
a1 + b1 + b2
a1 + b2
b2
a1
a1
a1
non-bonding
2s
O
Page 120
H2O
2H
Symmetry of Electronic States from NON-DEGENERATE MOs.

The ground electronic configuration for water is:
(a1)2(b2)2(b1)2(b2*)0(a1*)0
The symmetry of the electronic state arising from this configuration
is given by the direct product of the symmetries of the MOs of all
the electrons
(a1)2 = a1.a1 = A1
(b2)2 = b2.b2 = A1
(b1)2 = b1.b1 = A1
Page 121
For FULL singly degenerate

MOs, the symmetry is ALWAYS
A1

For FULL singly degenerate MOs, the symmetry is ALWAYS A1
(The totally symmetric species of the point group)
For orbitals with only one electron:
(a1)1 = A1, (b2)1 = B2, (b1)1 =B1
General rule:
For full MOs the ground state is always totally symmetric
Page 122

What happens if we promote an electron?
First two excitations move an electron form b1 non bonding
Into either the b2* or a1* anti-bonding orbitals .
a 1*
b2* Anti Bonding
b1
b2
a1
Page 123
Non bonding
Bonding
Both of these transitions are

non bonding to anti bonding
transitions. n-*
What electronic states do these new configurations generate?

(a1)2(b2)2(b1)1(b2*)1(a1*)0
= A1.A1.B1.B2 = A2
(a1)2(b2)2(b1)1(b2*)0(a1*)1
= A1.A1.B1.A1 = B1
In these states the spins can be paired or not.

IE: S the TOTAL electron spin can equal to 0 or 1.
The multiplicity of these states is given by 2S+1
These configurations generate:
3
A2 , 1A2 and 3B1 , 1B1 electronic states.
Page 124
Note: if S= then we have a doublet state

Molecular Orbitals
a 1*
b2*
Electronic States
B1
1
1
A2
b1
b2
a1
1
Page 125
B1
A2
A1

Triplet states are always lower than the related singlet states
Due to a minimisation of electron-electron interactions and
thus less repulsion
Between which of these states are electronic transitions
symmetry allowed?
Need to evaluate the transition moment integral like we did for
infrared transitions.
TM i* f d i f d
Page 126
Which electronic transitions are allowed?
TMI
V , f d
*
V ,i
Vibrational
S , f d
S ,i
Spin
e ,i
e, f d
Electronic
To first approximation can only operate on the electronic part

of the wavefunction.
Vibrational part is overlap between ground and excited state nuclear
wavefunctions. Franck-Condon factors.
Spin selection rules are strict. There must be NO change in spin
Direct product for electronic integral must contain the totally
symmetric species.
Page 127

A transition is allowed if there is no change in spin and the
electronic component transforms as totally symmetric.
The intensity is modulated by Franck-Condon factors.
The electronic transition dipole moment transforms as the
translational species as for infrared transitions.
Page 128

For the example of H20 the direct products for the
electronic transition are
B1
A2
A1 B2 A2 B2
A
B
1
1
B1
B1
A1 B2 B1 A1
A
A
1
2
The totally symmetric species is only present for the transition

to the B1 state. Therefore the transition to the A2 state is
symmetry forbidden
Transitions between singlet states are spin allowed.
transitions
between singlet and triplet state are spin forbidden.
Page
129
Symmetry
forbidden
Symmetry
allowed
Page 130
B1
A2
B1
A2
Spin forbidden
1
A1

Transitions between a totally symmetric ground state and one with
an electronic state that has the same symmetry as a component
of , will be symmetry allowed.
Caution: The lowest energy transition may be allowed but too weak
to be observed.
Caution: Ground state is not always totally symmetric and
beware of degenerate representations.
Page 131
More bonding for AX6 molecules / complexes

In the case of Oh point group:
d x2-y2 and dz2 transform as eg
dxy, dyz and dzx transform as t2g
px, py and pz transform as t1u
(ligands) = a1g + eg + t1u
(ligands) = t1g + t2g + t1u + t2u
Page 132
AX6 for Oh
4p
t1u
t1u*
a1g*
4s
a1g
eg*
3d
eg + t2g
t2g
eg
t1u
a1g
Page 133
a1g + eg + t1u
Electronic Spectroscopy of d9 complex:

[Cu(H2O)6]2+ is a d9 complex. That is approximately Oh.
Ground electronic configuration is: (t2g)6(eg*)3
Excited electronic configuration is : (t2g)5(eg*)4
The ground electronic state is 2Eg
Excited electronic state is 2T2g
Under Oh the transition dipole moment transforms as t1u
Are electronic transitions allowed between these states?
Page 134

Need to calculate direct product representation:
2
Oh
T2g
-1
t1u
-1
Eg
-1
DP
18
Page 135
C3
Eg . (t1u) . 2T2g
C2
-1
-1
-1
-1
-3
-1
-1
-18
-2
C2
S4
S6
C4

DP
18
-18
Use reduction formula: a p

g
-2
. ( R). p R
aa1g= 1/48 .[( 1x18x1)+(3x2x1) +(1x-18x1) +(3x-2x1)] = 0

The totally symmetric species is not present in this direct product.
The transition is symmetry forbidden.
We knew this anyway as g-g transitions are forbidden.
Transition is however spin allowed.
Page 136

Groups theory predicts no allowed electronic transition.
However, a weak absorption at 790nm is observed.
There is a phenomena known as vibronic coupling where the
vibrational and electronic wavefunctons are coupled.
This effectively changes the symmetry of the states involved.
This weak transition is vibronically induced and therefore is partially
allowed.
Page 137
Page 138
Are you familiar with symmetry elements operations?

Can you assign a point group?
Can you use a basis of 3 vectors to generate 3n ?
Do you know the reduction formula?
What is the difference between a reducible and irreducible
representation?
Can you reduce 3n ?
Can you generate vib from 3n ?
Can you predict IR and Raman activity for a given molecule using
direct product representation?
Can you discuss the assignment of spectra?
Can you use SALCs to describe the normal modes of SO2?
Can you discuss MO diagram in terms of SALCS?
Can you assign symmetry to electronic states and discuss whether
electronic transitions are allowed using the direct product
representation?
Given and infrared and Raman spectrum could you determine the
symmetry of the molecule?
http://www.chemsoc.org/exemplarchem/en
tries/2004/hull_booth/info/web_pro.htm
http://www.hull.ac.uk/php/chsajb/symmetry
&spectroscopy/ho_1.html
http://www.people.ouc.bc.ca/smsneil/sym
m/symmpg.htm
Page 139

SIMETRI S1 Kimia

Diunggah oleh

Informasi Dokumen

Judul Asli

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

SIMETRI S1 Kimia

Diunggah oleh

Hak Cipta:

Format Tersedia

Symmetry and Group Theory

Feature: Application for Spectroscopy

Unsur simetri dan operasi simetri molekul

Membiarkan obyek tidak

Rotasi seputar sumbu dengan

Refleksi melalui bidang simetri

Proyeksi melewati pusat

Sumbu rotasi tidak

Rotasi mengitari sumbu rotasi

Imperial College London

Rotations 360/n where n is an integer

Reflections for H2O

Examples: Benzene, XeF4

i element is a centre of symmetry

Mathematical Definition: Group Theory

A group is a collection of elements having certain properties

Steps to classify a molecule into a point group

Steps to classify a molecule into a point group

Steps to classify a molecule into a point group

Steps to classify a molecule into a point group

YES: Go to the Question 4

Steps to classify a molecule into a point group

Select Cn with highest n,

Select Cn with highest n,

Tugas I: Symmetry and Point Groups

KULIAH MINGGU III

Basic Properties of Groups

Any Combination of 2 or more elements of the collection must be

The combination of elements in the group must be ASSOCIATIVE

Example of Group Properties

It has E, C3 and C32

Any Combination of 2 or more elements of the collection must be equivalent to

where A, B and C are all members of the collection

Overall: C3 followed C3 gives C32

There must be an IDENTITY ELEMENT (E)

for all members of the collection

E commutes with all other members of the group

E. C32 = C32 and C32. C3 = E and C32. C32 = C3

The combination of elements in the group must be ASSOCIATIVE

C3 .(C3 .C32 )= (C3 .C3) C32

Group Multiplication Table

have an INVERSE which is also

The inverse of C32 is C3

KULIAH MINGGU IV-V

Imperial College London

Diagrams are cumbersome

Vectors are said to form the basis of the representation each

Constructing the Representation

Constructing the Representation

Constructing the Representation

Constructing the Representation

Constructing the Representation

py has the same symmetry properties as Ty and Rx vectors

Constructing the Representation

Constructing the Representation

Effects of symmetry operations generate the

Constructing the Representation:

Constructing the Representation

Constructing the Representation

The similarity transformation is such that

Constructing the Representation

This can generate very large matrices.

Character , = a11 + a22 + a33.