Character Table

The characters of the irreducible representations of a

point group are displayed in a table called Character Table

Sym. operations grouped by class

Point Group Symbol

C3V E 2C3 3sv

Orbital A1 1 1 1
Symmetry A2 1 1 -1
Types E 2 -1 0

Nomenclature (Mulliken)
A,B non-degenerate Characters:
E doubly degenerate +1 orbital is unchanged
T triply degenerate -1 orbital changes sign
0 more complicated change
Degeneracy: Number of symmetry related orbitals of of orbital
same energy
 Character Tables

The C3v character table

Symmetry operations

C3v E C3 C32 s v s v ' s ' 'v

1 1 1 1 1 1 1
2 1 1 1 −1 −1 −1
3 2 −1 −1 0 0 0

Irreducible The order h is 6

representations There are 3 classes
 Irreducible representations

Each irreducible representation of a group has a label called a symmetry species,

generally noted . When the type of irreducible representation is determined it is
assigned a Mulliken symbol:

One-dimensional irreducible representations are called A or B.

Two-dimensional irreducible representations are called E.
Three-dimensional irreducible representations are called T (F).

The basis for an irreducible representation is said to span the irreducible

representation.

Don’t mistake the operation E for the Mulliken symbol E!

 Irreducible representations

The difference between A and B is that the character for a rotation Cn is always
1 for A and -1 for B.

The subscripts 1, 2, 3 etc. are arbitrary labels.

Subscripts g and u stands for gerade and ungerade, meaning symmetric or

antisymmetric with respect to inversion.

Superscripts ’ and ’’ denotes symmetry or antisymmetry with respect to

reflection through a horizontal mirror plane.
Character Tables
 character Tables

There is a number of useful properties of character tables:

1. The sum of the squares of the dimensionality of all the irreducible
representations is equal to the order of the group
2. The sum of the squares of the characters multiplied by the number
of operations in the class in any irreducible representation is equal
to the order of the group.
3. The sum of the products of the corresponding characters of any two
different irreducible representations of the same group is zero.

4. The characters of all matrices belonging to the operations in the

same class are identical in a given irreducible representation.
C3 v E 2C3 3s v
5. The number of irreducible representations in a
group is equal to the number of classes of that 1 1 1 1
group. 2 1 1 −1
3 2 −1 0
 Reducible to Irreducible Representation

Let’s take an example :

N

1 3 2

To find the characters of the symmetry operations we look

at how many basis elements ”fall onto themselves” (or
their negative self) after the symmetry operation.

E: c=4 C3: c=1 sv: c=2

 Reducible to Irreducible Representation

So C3v in the basis will have the

following characters for the
N
different symmetry operations.

1 3 2

C3v E 2C3 3s v
red 4 1 2
 Reducible to Irreducible Representation

So C3v will have the following N

characters for the different symmetry
operations. 1 3 2

C3v E 2C3 3s v
Let’s add the red 4 1 2
character table of
the irreducible A1 1 1 1 By inspection we find
representation red=2A1+E
A2 1 1 −1
E 2 −1 0
 Reducible to Irreducible Representation

The decomposition of any reducible representation into

irreducible ones is uniqe, so if you find combination that
works it is right.

If decomposition by inspection does not work we have to

use results from the great and little orthogonality
theorems (unless we have an infinite group).
 Reducible to Irreducible Representation

1
ai =  g (c) c red (c) * c (l ) (c)
(l )

h l
Let’s go back to our example again. C3v E 2C3 3s v
red 4 1 2
a A1 = (1  4 1 + 2 1 1 + 3  2 1) = 2
1
A1 1 1 1
6 A2 1 1 −1

a A2 = (1  4 1 + 2 1 1 − 3  2 1) = 0
1 E 2 −1 0

6
aE = (1  4  2 − 2 1 1 + 3  2  0 ) = 1
1
6
So once again we find red=2A1+E
 Reducible to Irreducible Representation

1
ai =  g (c) c red (c) * c (l ) (c)
(l )

h l
Let’s go back to our example again. C3v E 2C3 3s v
red 4 1 2
a A1 = (1  4 1 + 2 1 1 + 3  2 1) = 2
1
A1 1 1 1
6 A2 1 1 −1

a A2 = (1  4 1 + 2 1 1 − 3  2 1) = 0
1 E 2 −1 0

6
aE = (1  4  2 − 2 1 1 + 3  2  0 ) = 1
1
6
So once again we find red=2A1+E
 Molecular Vibrations

Water

Molecular vibrations can always

be decomposed into quite simple
components called normal modes.

Water has 9 normal modes of which 3 are translational, 3

are rotational and 3 are the actual vibrations.

Each normal mode forms a basis for an irreducible

representation of the molecule.
 Molecular Vibrations

z3
z1
First find a basis for the
molecule. Let’s take the y3
x3 z2
cartesian coordinates for each y1
atom. x1
y2
x2
Water belongs to the C2v group which
contains the operations E, C2, sv(xz) and sv’(yz).

The representation becomes

E C2 sv(xz) sv’(yz)
red 9 -1 1 3
 Molecular Vibrations

Character table for C2v.

C2 v E C2 s v ( xz ) s 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 R2 xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz

C2 v E C2 s v ( xz) s v ' ( yz)

red 9 −1 1 3

Now reduce red to a sum of irreducible representations.

Use inspection or the formula.
 Molecular Vibrations

C2 v E C2 s v ( xz ) s 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz

The representation reduces to red=3A1+A2+2B1+3B2

trans= A1+B1+B2
rot=A2+B1+B2

vib=2A1+B2 Modes left for vibrations

 Molecular Vibrations

C2 v E C2 s v ( xz ) s 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz

Modes with translational symmetry will be infrared active

while modes with x2, y2 or z2 symmetry are Raman
active.

Thus water which has the vibrational modes

vib=2A1+B2 will be both IR and Raman active.