Character Tables

Decomposition of reducible representations into

irreducible representations
 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) List conventional symbols for irreducible representations:
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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 S with two and three dimensional representations
being P and D.
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 Mulliken symbols: Labelling

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 c = + 1 for the operation.)

If it is anti-symmetric with respect to the operation c = - 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 sv 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)

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 Mulliken symbols: Labelling

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 sh 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.

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Character Table (C2v)
Character Table (C2v)

The functions to the right are called basis

functions. They represent mathematical functions
such as orbitals, rotations, etc.
The px orbital
If a px orbital on the central
atom of a molecule with C2v
symmetry is rotated about the C2
axis, the orbital is reversed, so the
character will be -1.
The px orbital
If a px orbital on the central atom of a molecule with C2v symmetry is
rotated about the C2 axis, the orbital is reversed, so the character will be
-1.
The px orbital
If a px orbital on the central
atom of a molecule with C2v
symmetry is reflected in the yz
plane, the orbital is also reversed,
and the character will be -1.
The px orbital
If a px orbital on the central atom of a molecule with C2v symmetry is
reflected in the yz plane, the orbital is also reversed, and the character
will be -1.
The px orbital
If a px orbital on the central atom of a molecule with C2v symmetry is
reflected in the xz plane, the orbital is unchanged, so the character is +1.
Character Table Representations
1. Characters of +1 indicate that the basis function is unchanged by the
symmetry operation.
2. Characters of -1 indicate that the basis function is reversed by the
symmetry operation.
3. Characters of 0 indicate that the basis function undergoes a more
complicated change.
Character Table Representations
1. An A representation indicates that the functions are
symmetric with respect to rotation about the
principal axis of rotation.
2. B representations are asymmetric with respect to
rotation about the principal axis.
3. E representations are doubly degenerate.
4. T representations are triply degenerate.
5. Subscrips u and g indicate asymmetric (ungerade) or
symmetric (gerade) with respect to a center of
inversion.
 Symmetry of orbitals and functions
Oh E 8 C3 6 C2 6 C4 3 C2 i 6 S4 8 S6 3 sh 6 sd
(C42)
A1g 1 1 1 1 1 1 1 1 1 1 x2 + y2 + z2

A2g 1 1 -1 -1 1 1 -1 1 1 -1
Eg 2 -1 0 0 2 2 0 -1 2 0 (2z2 - x2 - y2,
x2 - y2)
T1g 3 0 -1 1 -1 3 1 0 -1 -1 (Rx, Ry,
Rz)
T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)

A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)

T2u 3 0 1 -1 -1 -3 1 0 1 -1
More notes about symmetry labels and characters:
-“T” indicates that the representation is triply-degenerate – this means that the functions grouped
in parentheses must be treated as a threesome and can not be considered individually.
-The subscripts g (gerade) and u (ungerade) in the symmetry representation label indicates
“symmetric” or “anti-symmetric” with respect to the inversion center, i.
Conversion of Reducible Representations
into Irreducible Representations

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 Generating Reducible Representations
Summarising we get that G3n for this molecule is:
C2v E C2 s(xz) s(yz)
G3n +9 -1 +1 3

To reduce this we need the character table for the point groups
C2v E C2 s(xz) s(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

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 Reducing Reducible Representations

1
We need to use the reduction formula: a p    n R .c ( R).c 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

c(R) is character of the reducible representation

cp(R) is character of the irreducible representation

nR is the number of operations in the class

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 C2 1E 1C2 1s(xz) 1s(yz)
v
A1 +1 +1 +1 +1 Tz x2, y2, z2 For C2v ; g = 4
A2 +1 +1 -1 -1 Rz xy and nR = 1 for
B1 +1 -1 +1 -1 Tx , Rx xz all operations

B2 +1 -1 -1 +1 Ty , Ry yz

C2v E C2 s(xz) s(yz)

G3n +9 -1 +1 3 1
a p    nR . c ( R ). c p R 
g R

aA1 = (1/4)[ ( 1x9x1) + (1x-1x1) + (1x1x1) + (1x3x1)] = (12/4) =3

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 1 s(xz) s(yz)
a p    nR . c ( R ). c p R 
C2v E C2
g R G3n +9 -1 +1 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

G3n = 3A1 + A2 + 2B1 + 3B2

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