NPTEL Chemistry and Biochemistry Coordination Chemistry (Chemistry of transition

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Irreducible Representations and Character

Tables
K.Sridharan
Dean
School of Chemical & Biotechnology
SASTRA University
Thanjavur 613 401

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Table of Contents
1Irreduciblerepresentationandcharactertables.........................................................................4
1.1
Irreduciblerepresentationandgettingthesymmetriesoftranslationsalongthe
differentaxes...............................................................................................................................4
1.1.1

Importanceofirreduciblerepresentation...................................................................4

1.1.2Translationalongthex,yandzaxesandirreduciblerepresentation................................4
1.1.2.1Translationalongthexaxis.............................................................................................4
1.2

Rotationalongthexaxis.....................................................................................................6

1.2.1Rotationalongthexaxis....................................................................................................6
1.3C2vCharacterTable...................................................................................................................7
2

Identifyingthesymmetriesoftranslationsalongtheaxesinsomeinorganicmolecules......9
2.1

D4hcharactertable........................................................................................................10

2.1.1Meaningof(x,y),(xz,yz)and(Rx,Ry)&C4operationonthetranslationalongthexaxis 10
2.1.2OperationEonthetranslationalongthexaxis...............................................................11
2.1.3C2operationonthetranslationalongxaxis....................................................................11
2.1.4EffectofC2operationonxandyvectors.......................................................................12
2.1.5EffectofC2onxandyvectors.......................................................................................13
2.1.6Effectofoperationionxandyvectors..........................................................................14
2.1.7EffectofS4operationonthexandyvectors.................................................................14
2.1.8Effectofhoperationonxandyvectors.......................................................................15
2.1.9Effectofvonxandyvectors.........................................................................................15
2.1.10Effectofdonxandyvectors......................................................................................16
2.1.11Identifyingthesymmetryoftranslationaboutxaxis....................................................17
3.1Deducingsymmetriesofrotationabouttheaxesfromirreduciblerepresentations.............18
3.1.1Rotationalongthezaxis..................................................................................................18
3.1.1.1EffectofEonrotationalongthezaxis.....................................................................18
3.1.1.2EffectofC2onrotationaboutzaxis..........................................................................18
3.1.1.3EffectofC2onrotationaboutzaxis.........................................................................18
3.1.1.4EffectofC2onrotationaboutzaxis.........................................................................19
3.1.1.5Effectofionrotationaboutzaxis............................................................................19
3.1.1.6EffectofS4onrotationaboutzaxis..........................................................................19
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3.1.1.7Effectofvonrotationaboutzaxis.........................................................................20
3.1.1.8Effectofdonrotationaboutzaxis..........................................................................20
3.1.1.9Effectofhonrotationaboutzaxis..........................................................................20
4ApplicationsofIrreducibleRepresentations..............................................................................21
5.References.................................................................................................................................24

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1 Irreducible representation and character tables

1.1 - Irreducible representation and getting the symmetries of
translations along the different axes
An irreducible representation contains characters which cannot be reduced
further to a simpler form. In other words, this is the simplest representation.of
characters of different symmetry operations.

1.1.1 Importance of irreducible representation

The point group of a molecule consists of a number of symmetry operations.
These symmetry operations constitute a mathematical group. It means that they
exhibit interrelationship as a collection. These mathematical relationships help us
in breaking each group into its irreducible representation.
These irreducible representations help us in analyzing molecular properties such
as optical activity, dipole moments and electronic properties such as IR and
Raman spectroscopy, electronic spectroscopy etc. Dynamic properties such as
translation, rotation etc can also be transformed by symmetry operations of the
point group of the molecule.

1.1.2 Translation along the x,y and z-axes and irreducible

representation
Let us consider water molecule. It has point group C2v. The symmetry operations
of this point group are E, C2, v(xz), and v(yz). Now we can see how the
translation along the three axes is transformed by these symmetry operations.
Z

Y
X

1.1.2.1 Translation along the x-axis

Translation is represented by an arrow along the respective axis for the atoms in
the given molecule. Let us consider water molecule as shown in Figure 1.1.2.1.
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C2

O
H

Fig 1.1.2.1 Water molecule translation along x-axis

Identity operation, E, does not change the directions of arrows. This is called
symmetric and the character is equal to +1
The C2 operation changes the directions of arrows 1800 opposite. This is called
antisymmetric and the character is equal to -1
O
H

The v(xz) operation is not changing the direction of the arrows along the x-axis
and hence the character is equal to +1
The v(yz) operation is not changing the directions of arrows 1800 opposite.
Hence, the character is -1.
Thus the characters of the four symmetry operations can be represented as
follows:
Symmetry operations:

C2

v(xz)

v(yz).

Characters:
+1
-1
+1
-1
From the C2v character table, it is can be seen that this irreducible representation
belongs to B1 symmetry.
Similarly, it can be shown that translation along the y-axis represents B2
symmetry and along z-axis represents A1 symmetry.
The numbers are called characters. Since these numbers cannot be reduced to
lower values, they are called irreducible representations.
This translation operation holds good for p - orbitals also because they can be
compared to arrows: the lobe with positive sign is similar to the head and the
lobe with negative sign can be compared to the tail of an arrow. Hence, the
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symmetry of a px orbital will be the same as that of translation along the x-axis,
that of the py orbital will be the same as that of the translation along the y-axis,
and that of the pz orbital will be the same as that of the pz orbital.

1.2 Rotation along the x-axis

A curved arrow (

) is taken as the basis vector for rotation to understand

the effect of different operations on it.

1.2.1 Rotation along the x-axis

Identity operation, E, does not change the directions of arrows. This is called
symmetric and the character is equal to +1
The C2 operation changes the directions of arrows 1800 opposite. This is called
antisymmetric and the character is equal to -1

The v(xz) operation changes the direction of the curved arrow and hence the
character is equal to -1.
The v(yz) operation does not change the direction of the curved arrow and
hence the character is equal to +1.

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Thus the characters of the four symmetry operations can be represented as

follows:
Symmetry operations:

C2

v(xz)

v(yz).

Characters:
+1
-1
-1
+1
From the C2v character table, it is can be seen that this irreducible representation
belongs to B2 symmetry. That is, the rotation about the x-axis belongs to B2
symmetry. Similarly, it can be shown that the rotation about the y-axis belongs to
B1 symmetry and that about the z-axis belongs to A2 symmetry.

1.3 C2v Character Table

C2v
A1
A2
B1
B2
II

E C2 v(xz) v(yz)
1 1 1
1
1 1 -1
-1
1 -1 1
-1
1 -1 -1
1
I

z
Rz
x, Ry
y, Rx
III

x2, y2, z2
xy
xz
yz
IV

On the left corner of the character table, the point group is shown. Any character
table has four main areas, I, II, III and IV.
Area I consists of the characters of the irreducible representations of the group.
Area II contains the Mulliken symbols. The meanings of 1.these symbols are
given below:
1. Symbols A and B are given to one dimensional representation, E to two
dimensional representation, and T to three dimensional representation.
2. When a one dimensional representation is symmetric with respect to
rotation by 2/n about the principal Cn axis, i.e., (Cn) = 1, symbol A is
given and B is given, if it is antisymmetric, (Cn) = -1.

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3. Subscripts 1 is attached to A and B, if the operation is symmetric to v or a

C2 perpendicular to the principal axis. and subscript 2 is attached if it is
antisymmetric .
4. Prime is attached to all letters,(A, B, etc.) if the operation is symmetric
with respect to h plane. Double prime is attached (A, B, etc.) if it is
antisymmetric.
5. If a group gas centre of inversion, then subscript g is used if it is
symmetric with respect to inversion and subscript u is used if it is
antisymmetric with respect to inversion.
Area III consists of symbols x, y, z, Rx, Ry, and Rz. These represent the
Cartesian coordinates and the rotations about the three axes. If two symbols
are placed within parentheses, [ex: (x,y), (Rx, Ry)], it means that both put
together form the basis and they cannot be separated.
Area IV contains the squares and binary products of the coordinates

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2 Identifying the symmetries of translations along the

axes in some inorganic molecules
Example 1: PtCl42x

y
C'2,

C"2,

Cl
Cl

Pt

Cl

C'2,

Cl
C4

C"2,

Symmetry elements present:

1. One C4 axis perpendicular to the plane of the paper (i.e. molecular plane)
2. Four C2 axes (two along the Pt-Cl bonds, shown as C2 and two along the
diagonals shown as C2
3. One h plane, that is the plane of the paper (molecular plane)
4. Two v planes containing the C2 . axes
5. Two d planes containing the C2 . axes
Hence, the point group is D4h

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2.1 D4h character table

D4h
A1g
A2g
B1g
B2g
Eg
A1u
A2u
B1u
B2u
Eu

E
1
1
1
1
2
1
1
1
1
2

2C4 C2
1
1
1
1
-1
1
-1
1
0
-2
1
1
1
1
-1
1
-1
1
0
-2

2C2
1
-1
1
-1
0
1
-1
1
-1
0

2C2
1
-1
-1
1
0
1
-1
-1
1
0

i
1
1
1
1
2
-1
-1
-1
-1
-2

2S4
1
1
-1
-1
0
-1
-1
1
1
0

h
1
1
1
1
-2
-1
-1
-1
-1
2

2v
1
-1
1
-1
0
-1
1
-1
1
0

2d
1
-1
-1
1
0
-1
1
1
-1
0

x2+y2, z2
Rz

x2-y2
xy
(Rx, Ry) (xz, yz)

z
(x,y)

2.1.1 Meaning of (x,y), (xz,yz) and (Rx,Ry) & C4 operation on the

translation along the x-axis
The symbol (x,y) means that translation along the x- and y-axes are inseparable
in a molecule with D4h symmetry and similarly operations on the the px and py
orbitals. The same explanation holds good for the rotation about x- and y-axes,
and the operations on the dxz and dyz orbitals.
Example:
Translation along the x-axis and along the y-axis are represented by arrows in
PtCl42- as shown in Figure 2.1.1.1

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2-

Fig 2.1.1.1 C4 operation & translation along the x- and y- axes in PtCl4

Thus both the vectors have changed positions in the C4 operation and the
character of this operation is equal to zero, i.e., (C4) = 0. Also, the vectors x and
y are inseparable because when an operation is done on x-vector, y-vector is
also affected. Hence, x and y are put in parentheses and written as (x,y).

2.1.2 Operation E on the translation along the x-axis

It is a doing nothing operation and the vectors are not disturbed from their
original positions. Hence, (E) = 2.

2.1.3 C2 operation on the translation along x-axis

The effect of C2 on the translation along the x-axis is shown in Figure 2.1.3.1.
The x- and y-vectors (arrows) are shifted to their negative coordinates. Hence,
(C2) = -2.

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Fig 2.1.3.1 Effect of C2 on the translation along the x-axis

2.1.4 Effect of C2 operation on x- and y-vectors

The C2 operation converts the x-vector into its negative and the y-vector remains
unchanged. Hence, (C2) = 0

Fig 2.1.4.1 Effect of C2 on the translation along the x-axis

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2.1.5 Effect of C2 on x- and y-vectors

The C2 operation interchanges the x- and y-vectors. Hence, (C2) = 0

Fig 2.1.5.1 Effect of C2 on the translation along the x-axis

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2.1.6 Effect of operation i on x- and y-vectors

The inversion operation, i,changes the x- and y-vectors into their negatives.
Hence, (i) = -2

Fig 2.1.6.1 Effect of i on the translation along the x-axis

2.1.7 Effect of S4 operation on the x- and y-vectors

This operation rotates the molecule by 900 and reflects in the molecular plane,
that is, the plane of the paper and (S4) = 0.

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Fig 2.1.7.1 Effect of S4 on the translation along the x-axis

2.1.8 Effect of h operation on x- and y-vectors

Reflection in the h plane does not affect the x- and y-vectors. Hence, (h) = 2

2.1.9 Effect of v on x- and y-vectors

The effect will be the same as that of C2 because v contains the C2 axis.
Hence, (v) = 0.

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Fig 2.1.9.1 Effect of v on the translation along the x-axis

2.1.10 Effect of d on x- and y-vectors

Dihedral plane d contains C2. Hence, the effect of d will be the same as that of
C2. Thus (d) = 0

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Fig 2.1.10.1 Effect of d on the translation along the x-axis

2.1.11 Identifying the symmetry of translation about x-axis

Now the characters of different operations can be given as follows:
2S4 h 2v 2d
D4h E 2C4 C2 2C2 2C2 i
2
0 -2
0
0
-2 0 2
0
0
This result is compared with D4h character table to find out the symmetry. It is
found that the symmetry is Eu. This appears in the character table as follows:
D4h E 2C4 C2 2C2 2C2 i
2S4 h 2v 2d
Eu 2
0 -2
0
0
-2 0 2
0
0 (x,y)
In the same way it can be shown that the translation about z-axis belongs to A2u
symmetry.

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3.1 Deducing symmetries of rotation about the axes

from irreducible representations
A curved arrow is used as the base vector for rotation.

3.1.1 Rotation along the z-axis

3.1.1.1 Effect of E on rotation along the z-axis

Fig 3.1.1.1.1 Effect of C4 on rotation about the z-axis

3.1.1.2 Effect of C2 on rotation about z-axis

This is nothing but doing C4 twice. The direction or the position of the arrow will
not be changed. Hence, (C2) = +1.

3.1.1.3 Effect of C2 on rotation about z-axis

The effect is shown in Figure 3.1.1.3.1. The direction of the curved arrow is
changed and hence, (C2) = -1
-z
Cl
Cl

Pt

Cl
Cl

C2

'

C2

'

Cl

Cl

Pt

Cl

Cl

C 4, z

Fig 3.1.1.1.3 Effect of C2 on rotation about the z-axis

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3.1.1.4 Effect of C2 on rotation about z-axis

The effect is the same as that of C2. (C2) = -1

3.1.1.5 Effect of i on rotation about z-axis

The direction of the curved arrow is not changed and shown in Figure 3.1.1.5.1
(i) = +1.

Fig 3.1.1.5.1 Effect of i on rotation about z-axis

3.1.1.6 Effect of S4 on rotation about z-axis

Cl
Cl

Pt

C4
Cl

Cl

Cl

C 4, z

Cl

Pt

Cl

Cl

Cl
Cl

Pt

Cl

Cl

C 4, z
Fig 3.1.1.6.1 Effect of S4 on rotation about z-axis

It is C4 operation followed by reflection in sh plane. The direction of the curved

arrow has not changed. Hence, (S4) = +1.

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3.1.1.7 Effect of v on rotation about z-axis

The v plane contains the C2 axis. The direction of the arrow changes as shown
in Figure 3.1.1.7.1. Hence, (v) = -1.

Fig 3.1.1.7.1 Effect of v on rotation about z-axis

3.1.1.8 Effect of d on rotation about z-axis

The d plane contains C2 axis. The effect is the same as C2 operation.

(d) = -1.

3.1.1.9 Effect of h on rotation about z-axis

The h plane is the molecular plane and the direction of the arrow is not
changed. Hence, (h) = +1.
Now the characters of the different operation are grouped as under.
D4h E 2C4 C2 2C2 2C2 i 2S4 h 2v 2d
1 1
1 -1
-1
1 1
1 -1
-1
When this is compared with D4h character table, it is found that this has got A2g
symmetry.

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D4h E 2C4 C2 2C2 2C2 i 2S4 h 2v 2d

A2g 1 1
1 -1
-1
1 1
1 -1
-1
Rz

Similarly, it can be shown that the rotation about x- and y-axis have Eg symmetry.

4 Applications of Irreducible Representations

It is a representation which can be further reduced to irreducible form. At first, the
reducible representation for a molecule is derived and then it is reduced. From
this irreducible representation we can find out the representations covering the
translation, rotation and vibration and from this we can find out the IR active and
Raman active vibrations.
Example: Trans-N2F2
Step 1: Structure of the molecule

Step 2:Symmetry elements present:

1. C2 axis
2. h plane
3. i
Step 3: Hence, the point group is C2h
Step 4:The C2h character table is given below

C2h E C2 i

Ag

Bg

-1

-1 Rx, Ry

Au

-1 -1 z

Bu

-1

-1 1

Rz

x2, y2, z2, xy

xz, yz

x, y

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Step 5:The number of operations in this group is four:

E, C2, i, h (as shown by the character table).
Step 6: The characters of the different operations are found out as follows:
Identity operation, E
All the 12 vectors (x,y,z) of the four atoms of the molecule are not disturbed.
Hence, the character, (E) = 12
C2 operation
All the four atoms are disturbed from their original places and occupy new
positions.
Hence, the character, (C2) = 0
i operation (inversion)
All the four atoms are displaced from their original positions to their new
positions.
Hence, (i) = 0
h operation (reflection in the horizontal plane of symmetry)
All the four atoms retain their original positions. Nothing is changed.

Let us consider the three x, y and z vectors (arrows) of one fluorine atom. When
reflected in the h plane (i.e. plane of paper), x and z arrows are not affected,
while the y-arrow is inverted.
Thus,
Old x = new x ; character = +1
Old y = - new y; character = -1
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Old z = new z; character = +1

Net character for one atom = +1
Hence, for four atoms, the total character will be equal to 4(+1) = +4.
Hence, (h) = 4.
Step 7: Hence the reducible representation is:
C2h E C2 i h

12 0 0 4
Step 8: This is reduced to get the components of this reducible representation
Ag = 1/4 [ (12)(1)(1) + 0 + 0 + (4)(1)(1) ] = 4
Bg = 1/4 [ (12)(1)(1) + 0 + 0 + (4)(-1)(1) ] = 2
Au = 1/4 [ (12)(1)(1) + 0 + 0 + (4)(-1)(1) ] = 2
Bu = 1/4 [ (12)(1)(1) + 0 + 0 + (4)(1)(1) ] = 4
Thus, = 4Ag + 2Bg + 2Au + 4Bu
From the character table, Au represents translation along the z-axis and Bu
represents that along the x- and y-axes. Thus, translation is given by Au + 2Bu.
Similarly, rotations are covered by the representations, Ag + 2Bg.
Translation + rotation are covered by Au + 2Bu + Ag + 2Bg.
This is subtracted from the total representation to find out the normal vibrations:
(4Ag + 2Bg + 2Au + 4Bu) . (Au + 2Bu + Ag + 2Bg) = 3Ag + Au + 2Bu
Of these,
IR active vibrations are Au + 2Bu = 3
Raman active vibrations are 3Ag = 3
Total vibrations = 6
The molecule is non-linear.
Hence, the number of expected vibrations =(3N-6) = (3x4.6) = 6.
Hence, this is correct.

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5. References
1. Inorganic Chemistry: Principles of Structure and Reactivity, James
E.Huheey, Ellen A.Keiter, Richard L.Keiter, Okhil K.Medhi, Pearson
Education, Delhi, 2006
2. Chemical Applications of Group Theory, 2/e, F.Albert Cotton, Wiley
Eastern, New Delhi, 1986

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