Simetri S1 Lengkap 2 SKS PDF

Symmetry and Group Theory
Feature: Application for Spectroscopy

and Orbital Molecules
Dr. Indriana Kartini
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
Marks
80% exam:
40% mid
50% final
10% group assignments of 4 students

Syllabus pre-mid: Prinsip dasar
Operasi dan unsur simetri

Sifat grup titik dan klasifikasi molekul dalam suatu grup titik
Matriks dan representasi simetri
Tabel karakter
Syllabus Pasca-mid: Aplikasi

prediksi spektra vibrasi molekul: IR dan Raman
prediksi sifat optik molekul
prediksi orbital molekul ikatan molekul
Page 3
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 4
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 5
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
F1
F2
F1
F3
Page 7
Reflections
Reflection is the operation
element is plane of symmetry
x is out of the plane
y
H2O
x
(xz)
H2
Page 8
H1
H1
H2
H2
H1
(yz)
Reflections for H2O

Page 9
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 10
XeF4
Reflections v
F
F
Xe
Xe
F
d
F
Xe
F
Page 11
XeF4
Page 12
Examples: Benzene, XeF4

Ethene
Inversion
i element is a centre of symmetry

Atom at (x,y,z)
Atom at (-x,-y,-z)
Z
Inversion , i
Y
X
X
Centre of inversion
Page 13
H
C
H
S4 Improper Rotation
Rotate about C4 axis and then reflect
perpendicular to this axis
H
S4
C4
Page 14
S4 Improper Rotation
Page 15
successive operation
Page 16
KULIAH MINGGU II
TEORI GRUP
Page 17
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 18
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 19

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 20
10

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 21

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 22
11

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 23
Molecule
Linear?
Dh
i?
2 or more
Cn, n>2?
Cv
i?
Ih
C5?
Oh
Td
*
Dnh
Dnd
Page 24
h?
nd?
Cn?
Select Cn with highest n,

nC2 perpendicular to Cn?
N
Dn
Cs
Cnh
h?
Cnv
nv?
S2n
S2n?
Ci
i?
C1
Cn
12
Benzene
Linear?
Dh
i?
2 or more
Cn, n>2?
Cv
i?
Ih
C5?
Oh
Td
*
Benzene
is D6h
Dnh
Dnd
Page 25
n=6
h?
nd?
Cn?
Select Cn with highest n,

nC2 perpendicular to Cn?
N
Dn
Cs
Cnh
h?
Cnv
nv?
S2n
S2n?
Ci
i?
C1
Cn
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 26
13
KULIAH MINGGU III
Page 27
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
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
Page 28
14
Example of Group Properties
H
B(OH)3 belongs to C3 point group
It has E, C3 and C32

symmetry operations
B
O
O
H
Page 29
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
O2
O1
C3
B
H1
O1
H3
H1
B
O3
H3
H3
O3
O3
C3
H2
O2
H2
O2
O1
H1
Overall: C3 followed C3 gives C32

Page 30
15
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
O2
H3
O1
O3
C32
H1
O1
C32
B
H1
AE= EA =A
O3
H2
O2
B
O1
H3
O3
H1
H3
O2
H2
E. C32 = C32 and C32. C3 = E and C32. C32 = C3

Page 31
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 .C3 = C32 ;
C3 .E = C3
C32 .C32 = C3
Operations are associative and E, C3 and C32 form a group
Page 32
16
Group Multiplication Table

Order of the group =3
C3
C3
C3
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 33
KULIAH MINGGU IV-V
Page 34
17
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
35
Math based
[1 2 3]
1
0
0
0
-1
0
0
0
1
36
18
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 37
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 38
19

A unit vector on each atom represents translation in the y direction
C2
S
O
S
O
C2.(Ty) = (-1) Ty
E .(Ty) = (+1) Ty
yz .(Ty) = (+1) Ty
xz .(Ty) = (-1) Ty
Page 39

A unit vector on each atom represents rotation around the z(C2) axis
S
O
O
C2.(Rz) = (+1) Rz
E .(RZ) = (+1) Rz
yz .(Rz) = (-1) Rz
xz .(RZ) = (-1) RZ
Page 40
20
C2v
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
Page 41

Use a mathematical function
Eg: py orbital on S
S
O
C2v
Page 42
O
E
C2
(xz)
(yz)
+1
-1
-1
+1
Ty,Rx
py has the same symmetry properties as Ty and Rx vectors
21
Au
Au
C4
[AuCl4]-
h.[d x2-y2] =
(+1) .[d x2-y2]
Au
C4.[d x2-y2] =
(-1) .[d x2-y2]
Page 43
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
2C4
C2
2C2 2C2 I
2S4
2v
2d
+1
-1
+1
+1
-1
+1
+1
-1
-1
+1
Page 44
22
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:
p x ' 0 1 p x
p ' =

y 1 0 p y
px
px py
py
py px
A 2x2 transformation
matrix
Page 45

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 46
23

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
b11 b21 0
b
21 b22 0
0
0 b33
The similarity transformation is such that

C-1 AC = B where C-1C=E
Page 47
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
B2
..
..
Bn
This can generate very large matrices.

However, all information is held in the character of these matrices
Page 48
24
Character Tables
a11
a
21
a 31
a12
a 22
a 32
a13
a 23
a33
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 49
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
C31, C31
v, v, v
are in the same class

are in the same class
Page 50
25
Character Tables an Example C3v : (NF3)
C3v
2C3 3v
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 51
Note:
You will not be asked to generate character tables.
These can be brought/supplied in the examination
Page 52
26
KULIAH MINGGU VI-VII-VIII
Page 53
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:
54
Mulliken symbols
27
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
being and .
Page 55

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

with respect to rotation about the highest order axis Cn.
(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 v plane. 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 56
28

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 57
Generating Reducible Representations

zs
z1
O
S
xs
ys
x1 x2
O
y1
x1
x2
xz
For the symmetry operation xz (a v )
z2
x2 x1 xs xs
y2
y1 -y2 y2 -y1 ys -ys
z1 z2
z2 z1
zs zs
Page 58
29

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

x2 1 0
( xz ) y2 = 0 1

z 2 0 0
x 0 0
s
y y 0 0
z 0 0
s
0 1
0 x1 x2
0 0 y1 y2
0 0 z1 z 2

0 0 x2 x1
0 0. y2 = y1

0 0 z 2 z1
0 0 xs xs

1 0 y s y s
0 1 z s z s
0 0
0 0 1 0 0
0 0
0 0
0
0
1 0
0 0
0 0
1 0
0
0
0 0
0 0
0 0
0 0
0
0
0 1
0 0
0 0
0 0
Page 59
x1 0 0
y 0 0
1
z1 0 0

x 2 1 0
( xz ) y2 = 0 1

z 2 0 0
x 0 0
s
y y 0 0

z s 0 0
0 1
0 0
0 0 1 0 0
0 0 0 1 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
0 0
0 0
0 x1 x2
0 0 y1 y2
0 0 z1 z 2

0 0 x2 x1
0 0. y2 = y1

0 0 z 2 z1
0 0 xs xs

1 0 y s y s
0 1 z s z s
0
Only require the characters: The sum of diagonal elements

For (xz) = + 1
Page 60
30
x1 1
y 0
1
z1 0

x2 0
( yz ) y2 = 0

z2 0
x 0
s
yy 0
z 0
s
0 0
0 0
1 0 0 0 0
0 1 0 0 0
0 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 x1 x1
0 0 0 y1 y1
0 0 0 z1 z1

0 0 0 x2 x2
0 0 0. y2 = y2

0 0 0 z 2 z 2
1 0 0 xs xs

0 1 0 y s y s
0 0 1 z s z s
0
For (yz) = + 3
Page 61
x1 1
y 0
1
z1 0

x2 0
E y 2 = 0

z 2 0
x 0
s
y y 0
z 0
s
0 0 0 0 0 0 0 0 x1 x1
1 0 0 0 0 0 0 0 y1 y1
0 1 0 0 0 0 0 0 z1 z1

0 0 1 0 0 0 0 0 x2 x2
0 0 0 1 0 0 0 0. y2 = y2

0 0 0 0 1 0 0 0 z 2 z 2
0 0 0 0 0 1 0 0 xs xs

0 0 0 0 0 0 1 0 y s y s
0 0 0 0 0 0 0 1 z s z s
For E = + 9
Page 62
31
x1 0 0
y 0 0
1
z1 0 0

x2 1 0
C2 . y2 = 0 1

z2 0 0
x 0 0
s
yy 0 0
z 0 0
s
0 1
0
0
0
0
0 0
1 0
0 1
0 x1 x2
0 0 0 y1 y2
0 0 0 z1 z 2

0 0 0 x2 x1
0 0 0. y2 = y1

0 0 0 z 2 z1
1 0 0 xs xs

0 1 0 y s y s
0 0 1 z s z s
0
For C2 = -1
Page 63

Summarising we get that 3n for this molecule is:
C2v
C2
(xz)
3n
+9
-1
+1
(yz)
3
To reduce this we need the character table for the point groups
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
Page 64
32
Reducing Reducible Representations
We need to use the reduction formula:
1
a p = n R . ( R). p (R )
g 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 65
C2
1E
1C2
1(xz) 1(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)
3n
+9
-1
+1
(yz)
3
For C2v ; g = 4 and nR = 1 for all operations
Page 66
33
1
a p = n R . ( R). p (R )
g R
C2v
C2
(xz)
3n
+9
-1
+1
(yz)
3
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 67
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
Contribution from these atoms
Page 68
34
Identity E
z
z1
E
y
y1
x
For each un-shifted atom
Page 69
x1
x1 1 0 0 x
y = 0 1 0. y
1

z1 0 0 1 z
(E) = +3
Inversion i
x1
z
y1
i
y
z1
x
x1 1 0 0 x
y = 0 1 0 . y
1

z1 0 0 1 z
(i) = -3
Page 70
35
Reflection (xz)
(Others are same except location of 1 changes)

z1
z
(xz)
y1
x1
x1 1 0 0 x
y = 0 1 0. y
1

z1 0 0 1 z
((xz)) = +1
Page 71
Rotation Cn
z1
z
Cn
y
x1
x
360/n
Page 72
360
360
cos n sin n 0
x
x
1
y = sin 360 cos 360 0. y
1 n

n
z1
0
0
1 z
y1
(Cn) = 1 + 2.cos(360/n)
36
Improper rotation axis, Sn
(xy)
Cn
y
x1
y1
x
360
360
cos n sin n 0
x1
x
y = sin 360 cos 360 0 . y
1 n

n
z1
0
0
1 z
Page 73
z1
(Sn) = -1 + 2.cos(360/n)
Summary of contributions from un-shifted atoms to 3n

R
(R)
+3
-3
+1
1+ 2.cos(360/n) C2
-1
1+ 2.cos(360/n) C3 ,C32
1+ 2.cos(360/n) C4, C4
0
+1
-1 + 2.cos(360/n) S31,S32
-2
S41,S42
-1
-1 + 2.cos(360/n)
-1 + 2.cos(360/n) S61,S65
Page 74
37
Worked example: POCl3 (C3v point group)

(R)
R
E
v
C3
Cl
2C3
3v
A1
A2
E
1
2
1
-1
-1
0
Un-shifted
atoms
Contribution
3
15
0
0
1
3
Page 75
3n
Cl
+3
+1
0
E
C3v
Cl
Number of classes,
(1 + 2 + 3 = 6)
Order of the group,
g=6
Reducing the irreducible representation for POCl3
1
a p = n R . ( R). p (R )
g R
C3v
3n
2C3
3v
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 76
38
KULIAH MINGGU IX-X-XI-XII

APLIKASI TEORI GRUP
Page 77
Group Theory and Vibrational Spectroscopy: SO2

C2
1E
1C2
1(xz) 1(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)
3n
+9
-1
+1
(yz)
3
3n = 3A1 + A2 + 2B1 + 3B2

Page 78
39
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
C2
1E
1C2
1(xz) 1(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
vib = 3n rot trans
3n = 3A1 + A2 + 2B1 + 3B2

rot =
A2 + B1 + B2
trans = A1
+ B1 + B2
vib = 2A1 + B2
(Degrees of freedom = 2 + 1 = 3 = 3n-6)
Page 79
Group Theory and Vibrational Spectroscopy: POCl3

3n
Cl
= 4A1 + A2 + 5E
trans = A1
rot =
vibe = 3A1
Cl
Cl
+ E
A2 + E
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 80
40
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 81
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 82
41
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
f
i
Wavefunction final state

Wavefunction initial state
Page 83
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 84
42
The DIRECT PRODUCT representation.

TM i* f d = i f d
(Tx )
( 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 85
C2
(xz) (yz)
C2V
A1
+1 +1
+1
+1
A2
+1 +1
Rz
B1
+1
+1
x, Ry
B2
+1
+1
y, R x
A1 B1 A1
+1
+1
B1
A1 B2 A1
+1
+1
B2
A1 A1 A1
+1 +1
+1
+1
A1
A1 B1 B 2
+1 +1
A2
A1 B2 B 2
+1 +1
+1
+1
A1
A1 A1 B2
+1
+1
B2
Page 86
43
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
We predict three bands in

the infrared spectrum of SO2
Page 87
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 88
44
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 89
Raman Spectroscopy
Virtual state
Stokes Shifted
=1 2
f
i

Wavefunction initial state
Page 90
45
Raman Spectroscopy
Anti-Stokes Shifted
Virtual state
=2 1
Wavefunction intial state
Page 91
Raman Spectroscopy
Probability of a Raman transistion:
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 92
46
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 93
Raman Spectroscopy The DIRECT PRODUCT representation

For SO2 group theory predicts only A1 and B2 modes
A1
A1

A2
A
A`1 A1 = 2
B
B
1
1
B
B
2
2
B2
A1

B
A2
A`1 B2 = 1
B
A
2
1
A
B
1
2
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 94
Note: A1 modes are polarised
47
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 95
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
r2
Determine the representation for stretch
Page 96
48

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 97

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 98
49
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:

=
1
2
(r1 + r2 )
Page 99
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:
1
(r1 r2 )
2
S
O
A1
O
B2
Sulphur must also move to maintain position of centre of mass

Page 100
50
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:
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
Page 102
51
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 103
Analysis of Vibrational Modes: POCl3
O
O
Cl
P
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
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 104
Six bands, Six co-incidences
52

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 105

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 106
53

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)
A1
193
Sym.
Deformation(1)
deformation
Page 107

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 108
54
Symmetry, Bonding and Electronic Spectroscopy
Use atomic orbitals as basis set.

Determine irreducible representations.
Construct QULATITATIVE molecular orbital diagram.
Calculate symmetry of electronic states.
Determine allowedness of electronic transitions.
Page 109

bonding in AXn molecules e.g. : water
How do 2s and 2p orbitals transform?
O 2s orbital
E, C2, xz, yx
O
H
O
H
C2V
C2
xz
yz
O2s
+1
+1
+1
+1
a1
Page 110
55

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 111

How do the 2p orbitals transform?
O 2p z orbital
+
O
H
E, C 2, xz, yx
C 2V
C2
xz
yz
O 2pz
+1
+1
+1
+1
a1
Page 112
56

How do the 2p orbitals transform?
O 2p y orbital
+
E, yx
C 2 , xz
H
C 2V
C2
xz
yz
O 2p y
+1
+1
b2
O 2px
+1
+1
b1
Page 113

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 114
57

Use the 1s orbitals on the hydrogen atoms
z
H 1s orbitals
O
H
+
H+
2
Page 115
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 116
58
Qualitative MO diagram for H2O

a1*
b2*
non-bonding (O 2px)
b1
a1 + b1 + b2
a1 + b2
b2
a1
a1
a1
non-bonding
2s
H2O
2H
Page 117

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 1 or 2 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 118
59
C2V
C2
xz
yz
a1
+1
+1
+1
+1
Sum and normalise
b2
+1
+1
Sum and normalise
pz
b2 = 1/2(1 2)
O
+
H+
1
Page 119
a1 = 1/2(1 + 2)
(a1)
+
+
py
H
2
(b2)

The overlap between the a1 orbitals (1) is greater than
that for the b2 orbitals (2).
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 120
60
Qualitative MO diagram for H2O

a1*
b2*
non-bonding (O 2px)
b1
a1 + b1 + b2
a1 + b2
b2
a1
a1
a1
non-bonding
2s
H2O
2H
Page 121
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
For FULL singly degenerate

MOs, the symmetry is ALWAYS
A1
A1.A1.A1 = A1
Page 122
61

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 123

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 .
a1 *
Anti Bonding
b2*
b1
b2
a1
Non bonding
Both of these transitions are

non bonding to anti bonding
transitions. n-*
Bonding
Page 124
62
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:
3A , 1A and 3B , 1B electronic states.
2
2
1
1
Note: if S= then we have a doublet state
Page 125

Electronic States
Molecular Orbitals
a1 *
b2*
b1
1B
1
1A
2
3B
1
3A
2
b2
a1
1A
1
Page 126
63
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 127
Which electronic transitions are allowed?
TMI *V ,i V , f d * S ,i S , f d *e,i e, f d
Vibrational
Spin
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 128
64

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 129

For the example of H20 the direct products for the
electronic transition are
A2
B1

A1 B2 A2 = B2
B
A
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
130
65

1
B1
A2
Symmetry
forbidden
Symmetry
allowed
B1
A2
Spin forbidden
1
A1
Page 131

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 132
66
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 133
AX6 for Oh
4p
t1u
t1u*
a1g*
4s
a1g
eg*
3d
eg + t2g
t2g
eg
a1g + eg + t1u
t1u
a1g
Page 134
67
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 135

Need to calculate direct product representation:
2E
g
. (t1u) . 2T2g
i
6S
4
8S
6
-1
-1
-1
-1
-3
-1
-1
-18
-2
Oh
8C
T2g
-1
t1u
-1
Eg
-1
DP
18
6C
6C
3C
Page 136
68

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 137

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 138
69
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?
Page 139
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 140
70

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Symmetry and Group Theory

Feature: Application for Spectroscopy

Dr. Indriana Kartini

10% group assignments of 4 students

Operasi dan unsur simetri

Syllabus Pasca-mid: Aplikasi

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

Because of the symmetry of molecules they can

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

Operations are associative and E, C3 and C32 form a group

Group Multiplication Table

Every member of the group must

have an INVERSE which is also

The inverse of C32 is C3

KULIAH MINGGU IV-V

Imperial College London

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