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Irreducible Representations and Character Tables
Irreducible Representations and Character Tables
elements)
K.Sridharan
Dean
SASTRA University
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Table of Contents
1 Irreducible representation and character tables ......................................................................... 4
1.1 ‐ Irreducible representation and getting the symmetries of translations along the
different axes ............................................................................................................................... 4
1.1.1 Importance of irreducible representation ................................................................... 4
1.1.2 Translation along the x,y and z‐axes and irreducible representation ................................ 4
1.1.2.1 Translation along the x‐axis ............................................................................................. 4
1.2 Rotation along the x‐axis ..................................................................................................... 6
1.2.1 Rotation along the x‐axis .................................................................................................... 6
1.3 C2v Character Table ................................................................................................................... 7
2 Identifying the symmetries of translations along the axes in some inorganic molecules ...... 9
2.1 D4h character table ........................................................................................................ 10
2.1.1 Meaning of (x,y), (xz,yz) and (Rx,Ry) & C4 operation on the translation along the x‐axis 10
2.1.2 Operation E on the translation along the x‐axis ............................................................... 11
2.1.3 C2 operation on the translation along x‐axis .................................................................... 11
2.1.4 Effect of C2’ operation on x‐ and y‐vectors ....................................................................... 12
2.1.5 Effect of C2” on x‐ and y‐vectors ....................................................................................... 13
2.1.6 Effect of operation i on x‐ and y‐vectors .......................................................................... 14
2.1.7 Effect of S4 operation on the x‐ and y‐vectors ................................................................. 14
2.1.8 Effect of h operation on x‐ and y‐vectors ....................................................................... 15
2.1.9 Effect of v on x‐ and y‐vectors ......................................................................................... 15
2.1.10 Effect of d on x‐ and y‐vectors ...................................................................................... 16
2.1.11 Identifying the symmetry of translation about x‐axis .................................................... 17
3.1 Deducing symmetries of rotation about the axes from irreducible representations ............. 18
3.1.1 Rotation along the z‐axis .................................................................................................. 18
3.1.1.1 Effect of E on rotation along the z‐axis ..................................................................... 18
3.1.1.2 Effect of C2 on rotation about z‐axis .......................................................................... 18
3.1.1.3 Effect of C2’ on rotation about z‐axis ......................................................................... 18
3.1.1.4 Effect of C2” on rotation about z‐axis ......................................................................... 19
3.1.1.5 Effect of i on rotation about z‐axis ............................................................................ 19
3.1.1.6 Effect of S4 on rotation about z‐axis .......................................................................... 19
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3.1.1.7 Effect of v on rotation about z‐axis ......................................................................... 20
3.1.1.8 Effect of σd on rotation about z‐axis .......................................................................... 20
3.1.1.9 Effect of σh on rotation about z‐axis .......................................................................... 20
4 Applications of Irreducible Representations .............................................................................. 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.
Z
Y
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z
C2
O y
H H
x
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 H
The σv(xz) operation is not changing the direction of the arrows along the x-axis
and hence the character is equal to +1
The σv(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: E C2 σv(xz) σv(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.
The σv(xz) operation changes the direction of the curved arrow and hence the
character is equal to -1.
The σv(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: E C2 σv(xz) σv(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.
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 II contains the Mulliken symbols. The meanings of 1.these symbols are
given below:
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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.
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2 Identifying the symmetries of translations along the
axes in some inorganic molecules
Example 1: PtCl42-
y
C'2, v
z C"2, d
Cl
Cl Pt Cl C'2, v
Cl
C4
C"2, d
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2.1 D4h character table
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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., χ(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).
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Fig 2.1.3.1 Effect of C2 on the translation along the x-axis
’
Fig 2.1.4.1 Effect of C2 on the translation along the x-axis
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”
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, χ(i) = -2
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.
Fig 2.1.9.1 Effect of σv on the translation along the x-axis
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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:
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.
Fig 3.1.1.1.1 Effect of C4 on rotation about the z-axis
-z
Cl Cl
'
C2
'
Cl Pt Cl C2 Cl Pt Cl
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’. χ(C2’’) = -1
Cl Cl h Cl
C4
Cl Pt Cl Cl Pt Cl Cl Pt Cl
Cl Cl Cl
C 4, z C 4, z
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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, χ(σv) = -1.
χ(σd) = -1.
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D4h E 2C4 C2 2C2’ 2C2” i 2S4 σh 2σv 2σd
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.
C2h E C2 i σh
Ag 1 1 1 1 Rz x2, y2, z2, xy
Bg 1 -1 1 -1 Rx, Ry xz, yz
Au 1 1 -1 -1 z
Bu 1 -1 -1 1 x, y
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Step 5:The number of operations in this group is four:
E, C2, i, σh (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, χ(E) = 12
C2 operation
All the four atoms are disturbed from their original places and occupy new
positions.
Hence, the character, χ(C2) = 0
i operation (inversion)
All the four atoms are displaced from their original positions to their new
positions.
Hence, χ(i) = 0
σh 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 σh 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, χ(σh) = 4.
Step 7: Hence the reducible representation is:
C2h E C2 i σh
Γ 12 0 0 4
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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
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