1 Lecture presentation

GROUP THEORY IN A NUTSHELL

Dr. Cyriac Mathew
Associate Professor

Study Points (SP)

SP 1
Point Group


Point groups are possible combinations of symmetry elements. The group sometimes include
only essential (necessary to define the group) symmetry elements, and sometimes redundant
symmetry elements also. All these symmetry elements of a group intersect at some point.
Hence the name point group. Since the symmetry elements can combine only in a definite
pattern, there will only a finite number of symmetry elements possible. For crystals only 32
point groups exist. Molecular point groups are represented by Schoenflies notations and
crystallographic point groups are represented by Hermann-Mauguin notations.

SP 2
Important!


The symmetry elements constituting a point group give rise to a large number of symmetry
operations depending on the point group. These symmetry operations form a mathematical
group obeying the group theoretical rules. The number of symmetry operations avoiding
redundancy (repeating) is called the order of the group, h. The symmetry operations that form
a group, are called the elements of the group (do not confuse with symmetry elements).

SP 3
Another
definition for
point group
Point group is a collection of symmetry operations that obeys the mathematical rules for the
formation of a group. During symmetry operations the centre of mass does not shift and hence
the name point group.

SP 4

Group
theoretical rules


Rule 1: The combination or product of two elements of a group is an element of the same
group.
Rule 2: Every group contains one element which commutes with every other elements and
leave them unchanged.
Rule 3: The associative law of multiplication is followed
Rule 4: For every element of the group there is an inverse which is also an element of the same
group.
SP 5
Abelian group

A group in which every two elements commute with each other is called an Abelian group. For
such groups the group multiplication table will be symmetric with respect to the diagonal. Eg.
C
2v
. (Named after Neils Abel, a Norwegian Mathematician)
SP 6
Cyclic group
If all the element of a group can be derived from one basic element of the group, the group is
called a cyclic group. Eg. C
3

SP 7
Similarity
transformation
Let A, B and C be elements of the same group. Then, if C
1
AC = B, A and B are said to be
conjugate elements. A and C should not commute with each other. If they commute the
similarity transformation will give the same element.
SP 8
Class of elements
A set of conjugate elements is called a class of elements, and similarity transformation is the
procedure for classification of elements into classes.
SP 9
Inverse
(should
remember)

E
1
= E
o
1
= o
i
1
= i
C
n
1
= C
n
(n1)
or
{ }
1
( 1) n
n n
C C

=
S
n
1
= S
n
(n1)
, when n is even
S
n
1
= S
n
(2n1)
, when n is odd
SP 10
Methods to
identify classes

SP 11
1. E, o
h
and i commute with all symmetry elements, hence form separate classes
2. The principal axis C
n
and its inverse C
n
1
belong to the same class if a o
v
is present or a C
2
r
to C
n
is present.
3. The symmetry elements S
n
and S
n
1
belong to the same class if a o
v
is present or a C
2
r
to S
n
is present.
2 Lecture presentation

Point group
(molecular)
Essential
symmetry
elements
Elements (operations) of the
group (elements of same class
are shown in brackets).
Order Class Example
C
1
E E (=C
1
) 1 1 CHBrClF
C
s
E, o E, o 2 2
Quinoline,
C
i
E, i E, i (= S
2
) 2 2 trans-CFClBrCFClBr
C
2
E, C
2
E, C
2
2 2 Hydrogen peroxide
C
3
E, C
3
E, C
3
1
, C
3
2
3 3 Phosphoric
acid
C
4
E, C
4
E, C
4
, C
2
, C
4
3


4 4

C
5
E, C
5
E, C
5
, C
5
2
, C
5
3
, C
5
4
5 5
C
6
E, C
6
E, C
6
, C
3
, C
2
, C
3
2
, C
6
5
6 6
C
2v
E, C
2
, 2o
v
E, C
2
, o
v
(xz), o
v
(yz) 4 4 Water
C
3v
E, C
3
, 3o
v
E, (C
3
, C
3
2
), (o
v
,o
v
, o
v
) 6 3 Ammonia
C
4v
E, C
4
, 4o
v
E, (C
4
, C
4
3
), C
2
,(o
v
,o
v
),(o
d
,o
d
) 8 5 IF
5

C
5v
E, C
5
, 5o
v
E, (C
5
,C
5
4
), (C
5
2
, C
5
3
), (5o
v
) 10 4
C
2h
E, C
2
, o
h
E, C
2
, o
h
, i 4 4 trans-1,2-dichloroethene
C
3h
E, C
3
, o
h
E, C
3
, C
3
2
, o
h
, S
3
1
, S
3
5
6 6 Boric acid
C
4h
E, C
4
, o
h
E, C
4
, C
2
, C
4
3
, i, S
4
3
, o
h
,S
4
8 8

C
5h
E, C
5
, o
h
E, C
5
, C
5
2
,C
5
3
,C
5
4
, o
h
,S
5
, S
5
7
, S
5
3
,
S
5
9

10 10
D
2
E, C
2
, 2C
2
r E, C
2
(z), C
2
(x), C
2
(y) 4 4 Cycloocta-1,5-diene
D
3
E, C
3
, 3C
2
r E, (C
3
, C
3
2
), (C
2
, C
2
, C
2
) 6 3 [S
2
O
6
]
2

D
2h
E, C
2
, 2C
2
r, o
h
E, C
2
(z), C
2
(x), C
2
(y), o
h
, o
v
,o
v
,
i(=S
2
)
8 8

D
3h
E, C
3
, 3C
2
r, o
h
E, (C
3
, C
3
2
), (C
2
, C
2
, C
2
), o
h
,
(S
3
, S
3
5
), (o
v
,o
v
, ,o
v
)
12 6

D
4h
E, C
4
, 4C
2
r, o
h
E, (C
4
, C
4
3
), C
2
, (C
2
, C
2
)
(C
2
,C
2
), (S
4
, S
4
3
), i, o
h

(o
d
,o
d
), (o
v
,o
v
)
16 10

D
5h
E, C
5
, 5C
2
r, o
h
E, (C
5
, C
5
4
), (C
5
2
, C
5
3
), 5C
2
, o
h
,
(S
5
, S
5
9
), (S
5
3
, S
5
7
), 5o
v

20 8 Eclipsed ferrocene, C
70
, C
50

D
6h
E, C
6
, 6C
2
r, o
h
E, (C
6
, C
6
5
), (C
3
, C
3
2
), C
2
, 3C
2
,
3C
2
, i, o
h
, (S
6
, S
6
5
), (S
3
, S
3
2
),3o
d
,
3o
v

24 12

D
2d
E, C
2
, 2C
2
r, 2o
d
E, C
2
, (S
4
, S
4
3
), (C
2
,C
2
), (o
d
,
o
d
)
8 5 allene
D
3d
E, C
3
, 2C
2
r, 3o
d
E, (C
3
, C
3
2
), (C
2
,C
2
, C
2
), (S
6
,
S
6
5
), i, (o
d
, o
d
, o
d
)
12 6
cyclohexane (chair)
C
v
E, C

, o
v
E, C

, o
v
HCl
D
h
E, C

, C
2
r, o
h
E, C

, C
2
, o
h
, i, o
v
CO
2

T
d
E, C
3
,C
2
,S
4
, o
d
E, 8C
3
,3C
2
,6S
4
, 6o
d
24 5 Methane
O
h
E, C
3
,C
2
, C
4
, C
2
(=C
4
2
), i, S
4
,S
6
,
o
h
, o
d

E, 8C
3
,6C
2
, 6C
4
, 3C
2
(=C
4
2
), i,
6S
4
,8S
6
, 3o
h
, 6o
d

48 10 SF
6

3 Lecture presentation

SP12
Symmetry
operations and
matrices
Symmetry operations can be conveniently represented by matrices. Similar to symmetry
operations,
1. Multiplication of two matrices give another matrix
2. Multiplication of a matrix with unit matrix is commutative and leaves the matrix
unchanged
3. The associative law is valid for matrix multiplication
4. A matrix has an inverse.
SP13
Matrix
representations
for (i) and (E)
Inversion (i)
1 0 0
0 1 0
0 0 1

(
(

(
(

Identity (E)
1 0 0
0 1 0
0 0 1
(
(
(
(


SP14
Matrix
representations
for (o)
o
xy
(o
h
)
1 0 0
0 1 0
0 0 1
(
(
(
(

o
xz

1 0 0
0 1 0
0 0 1
(
(

(
(

o
yz

1 0 0
0 1 0
0 0 1

(
(
(
(


SP15
Matrix
representations
for C
2
, C
n
and S
n

C
2
(z)


1 0 0
0 1 0
0 0 1

(
(
(
(

C
n
(z)

cos sin 0
sin cos 0
0 0 1
u u
u u

(
(
(
(

C
n
(z)

cos sin 0
sin cos 0
0 0 1
u u
u u
(
(

(
(



SP16
Matrix
representation
for S
n

S
n

cos sin 0
sin cos 0
0 0 1
u u
u u

(
(
(
(


SP16
Matrix
representation
of group
A representation of the point group can be obtained through a set of matrices, each of which
corresponds to a single symmetry operation in the group. Thus, a set of matrices, each of which
stands for an element of a group and which combine among themselves the same way as the
group elements combine is called a group representation or matrix representation.
SP17
How to set up
the
representation?
One procedure for obtaining a representation is to carry out symmetry operations on a position
vector in a body. For C
2v
point group the four symmetry operations are, E, C
2
, o
v
, o
v
. Taking
H
2
O as an example, by assigning Cartesian coordinates to each atom and performing the
operations we will get a 9x9 matrix for each operation.
b
b
C2
a
a
x1
-x1
z1
z1
C2
C2[(x1y1z1)(x2y2z2)(x3y3z3)]
-x2
(x1'y1'z1')(x2'y2'z2')(x3'y3'z3')
z3
x2
-x3
z3
-y2
x3
-y3
y2
z2
y3 -y1
z2
y1






The corresponding matrix product is

(anti-
clockwise)
(clockwise)
During C
2
operation H
a
and H
b
get exchanged
so that x
1
,y
1
, z
1
x
3
,y
3
,z
3
and vice versa
4 Lecture presentation





'
1 1
'
1 1
'
1 1
'
2 2
'
2 2
'
2 2
'
3 3
'
3 3
'
3 3
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 1 0 0 0 0 0
0 0 0 0 1 0 0 0 0
0 0 0 0 0 1 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
x x
y y
z z
x x
y y
z z
x x
y y
z z
( (
( (

( (
( (
( (

( (
( ( =
( (
( (
( (

( (

( (
( (

(
(
(
(
(
(
(
(
(
(
(
(
(

Transformation matrix
The dimension and complexity of matrices in a group representation will depend on the system
we take as the basis. (The number of atoms present in the molecule). For example pyridine
molecule has C
2v
symmetry with 11 atoms. If each atom is assigned three unit vectors along x, y,
and z axes, it is possible to write down 33x33 matrix. This dimensionality of a matrix is quite big
and is certainly unwieldy.
SP18
Reduction of
representation
The procedure of conversion of a matrix of a larger dimension into smaller dimensional
matrices is called reduction.
SP19
Reducible
representation
If the matrix of a group representation can be reduced to smaller dimensional matrices, such
representations are called reducible representations (RRs).
SP20
Irreducible
representation
Group representations can be reduced to smaller dimensions through similarity transformation.
It renders diagonal matrices which are then block factored. If by such reduction procedure we
reach at group representation consisting of matrices which cannot be reduced further, we call
the representation as irreducible representation (IR).
Reduced matrices for different operations with identical dimensions are written in a row. This
forms one IR.
For any symmetry group, only a finite number of representations of smaller dimensions are of
fundamental importance. These are the irreducible representations and are non-equivalent.
The nature and number of the IRs are characteristic of a point group and the IRs remain the
same for different types of molecules, provided they belong to the same point group.
SP21
Character of
Irreducible
representation
To make the representation further simpler we list the character of matrices of irreducible
representations. The character of a one dimensional group representation will simply be the
element of the matrices. For two and three dimensional representations the character will be
the sum of the diagonal elements of the matrices.
SP22
The great
orthogonality
theorem (GOT)
Give the relation between elements of the matrices constituting the irreducible representation
of a group.
' ' ' '
( )
( )
i R mn ij
j R mn mm nn
R
i j
h
l l
o o o I I =

where,
' '
' '
' '
' '
1, when , 1, , 1
0, , 0, , 0
ij
mm nn
ij
mm nn
i j when m m when n n
when i j when m m when n n
o o o
o o o
= = = = = =
= = = = = =

( ) i R mn
I =The element in the m
th
row and n
th
column of the matrix corresponding to an
operation (R) in the i
th
irreducible representation.
( ) j R mn
I = The element in the m
th
row and n
th
column of the matrix corresponding to an
operation (R) in the j
th
irreducible representation.





5 Lecture presentation

SP23
Rules derived
from GOT for
constructing
character tables
Rule 1: The number of IRs in a group is equal to the number of classes of elements in the group
Rule 2: In a given representation the characters of all the elements of the same class will be
identical.
Rule 3: The sum of the squares of the dimensions of the IRs of a group will be equal to order of
the group.
2
i
l h =

Rule 4: The sum of the squares of the characters of in a given IR is equal to the order of the
group.
Rule 5: The characters of any two IRs of a group are orthogonal.
SP24 Since the character of the identity element is the same as the dimension of IRs, the sum of the
squares of characters of E in a group is equal to h.
ie.
2
( ) i E
h _ ( =

SP25 For every point group there can be one IR with all characters equal to 1. This is given as the first
IR of the group (
1
I ).
SP26
Mullikkans
symbol for IRs
Mullikkans symbols are derived on the basis of the following rules.
1. One dimensional IR will be represented by A or B, two dimensional by E and three
dimensional by T.
2. One dimensional representations symmetric to principal axis (character +ve) are
denoted by A, and those are anti-symmetric (character ve) are denoted by B
3. Symmetric or anti-symmetric nature with respect to C
2
r to C
n
is denoted by subscripts
1 and 2 respectively. If C
2
r to C
n
is absent the subscripts 1 and 2 denote symmetric or
anti-symmetric nature with respect to vertical plane (the first appearing in the CT)
4. Single prime and double prime are used to denote symmetric or anti-symmetric nature
with respect to horizontal plane.
5. In groups with centre of symmetry, symmetric or anti-symmetric nature with respect to
inversion is indicated with a subscript g or u.
Point groups where both i and o
h
are present, the IRs are preferably labeled after subscripts
g or u.
Subscripts for E and T are more complicated.
SP27
Character table
(CT)
Character table has four areas:
Area I: characters of matrices of IRs for various operations of the group.
Area II: the Mullikkans symbols for IRs
Area III: Contains rotational (R
x
, R
y
, R
z
) and linear (x, y, z) functions which represent both the
translational vectors and p-orbitals.
Area IV: squares and binomial products of x, y, z coordinates. These functions represent both
the polarizability parameters and d-atomic orbitals.
SP28
Character of
reducible
representation
The character of the reducible representation for any symmetry operation (R) is given by,

R
= (no. of atoms that do not shift when a symmetry operation (R) is performed) (character
corresponding to the symmetry operation (R) in a general 33 matrix representation)
SP29
Number of times
of occurrence of
a particular IR
Once we know the reducible representation we can find out the number of times (n
i
) each IR
occur in it, provided we know the character table.
( ) ( ) ( )
1
i R i R R
n g
h
_ _ =


n
i
= the number of times the i
th
IR occurring in the reducible representation
h = order of the group
i(R)
= the character of the operation (R) in the i
th
IR
(R)
= the corresponding character in the reducible representation (total character)
g
(R)
= number of conjugate elements occurring in the class of the element R


Appendix
Matrices
6 Lecture presentation

A matrix is a rectangular array of numbers or symbols for numbers. Matrix A = [a
ij
]
4 4
1 3 0 1
5 0 7 1
2 3 4 7
0 1 1 0

(
(
(
(
(


Different types of matrices
1. Rectangular matrices: Matrix where mn
2. Column matrix: matrices with a single column. Vectors are represented by column matrices. Eg. the Cartesian
system of coordinates,
x
y
z
x
y
z

3. Row matrix: single row, [23456]
4. Null matrix:
0 0 0
0 0 0
0 0 0
(
(
(
(


5. Square matrix: m = n, symmetry operations are represented by square matrices
6. Diagonal matrix: All elements zero except diagonal elements in a square matrix
1 0 0
0 5 0
0 0 2
(
(
(
(


7. Scalar matrix:
5 0 0
0 5 0
0 0 5
(
(
(
(


8. Identity matrix: all diagonal elements unit in a square matrix,
1 0 0
0 1 0
0 0 1
(
(
(
(


9. Two matrices are said to be equal if the corresponding elements are the same.
11 12
21 22
2 0
,
1 3
a a
A B
a a
( (
= =
( (


. A = B if, a
11
= 2, a
12
= 0, a
21
= 1, a
22
= 3
10. Matrix multiplication
1 2 1 2 3 1(1) 2(4) 1(2) 2(5) 1(3) 2(6)
and AB =C, C =
3 4 4 5 6 3(1) 4(4) 3(2) 4(5) 3(3) 4(6)
2 12 15
19 26 33
B
+ + +
( ( (
= =
( ( (
+ + +

(
=
(


The product of two matrices A and B is defines if the number of columns of A is equal to number of rows of B.
11. Character of a matrix: the sum of diagonal elements.
7 Lecture presentation

1 2 1
3 1 4
1 0 3
A
(
(
=
(
(

_(A) = 3

12. Inverse of a square matrix: if A is a square matrix of order m and B another square matrix order m, then B is
called the inverse of A if AB = BA = I, (identity matrix). That is B = A
1
. Or A A
1
= I (identity)

13. Diagonalization of matrix: carried out by similarity transformation

P
1
AP = D (diagonal matrix)

14. Simultaneous equations can be written as matrix product:


3x + 2y z = x
2x + 0y +z = y
x + 2y +3z = z

(x,y,z) (x,y,z)


15. Block factorization of large matrices

AB = C
1 0 0 0 0 0 2 2 0 0 0 0 2 2 0 0 0 0
1 1 0 0 0 0 1 1 0 0 0 0 1 1 0 0 0 0
0 0 2 1 0 0 0 0 1 1 0 0 0 0 2 1 0 0
0 0 1 0 0 0 0 0 0 1 0 0 0 0 1 1 0 0
0 0 0 0 0 1 0 0 0 0 3 2 0 0 0 0 4 2
0 0 0 0 1 0 0 0 0 0 4 0 0 0 0 0 3 2
( ( (
( ( (

( ( (
( ( (
=
( ( (

( ( (
( ( (
( ( (

[A] [B] [C]
=

Sub
matrices
=
A1
A2
A3
B1
B2
B3
C1
C2
C3
[A1][B1] = [C1]
[A2][B2] = [C2]
[A3][B3] = [C3]

16. Reducible and irreducible representations: Let ABC ..E be the matrix representation of a group and P be a
similarity transformation matrix then,

P
1
EP = E, P
1
AP = A, P
1
BP = B, P
1
CP = C. E, A, B, and C are diagonal matrices that can be block factored.
E1'
E2'
E3'
[E'] =
[A'] =
[B'] =
B1'
[C'] =
A1' C1'
B2' A2' C2'
B3' A3' C3'

The sub-matrices E
1
, A
1
, B
1
C
1
will have identical dimensions. So also E
2
, A
2
, B
2
C
2
. Now the
representation of the group will be,

1
= [E
1
][ A
1
][ B
1
][ C
1
] ..

2
= [E
2
][ A
2
][ B
2
][ C
2
] ..

These sub-matrices cannot be further reduced. Hence the above representation is the irreducible
representation of the group.


3 2 1 '
2 0 1 '
1 2 3 '
x x
y y
z z

( ( (
( ( (
=
( ( (
( ( (


Transformation matrix