Matrix Approach for the Derivation of the Character Table

Ramakrishna Podilaa)
Dept. of Physics and Astronomy, Clemson University, Clemson,
SC 29634

(Dated: 30 April 2010)

ABSTRACT: A character table can predict the number and nature of Raman and
infra-red active modes of a given system. It is generally derived by applying the rules
of group theory on the possible symmetry oprations for a given molecule. However, an
equivalent approach using matrices can also be used in the case of simple molecules
(such as AX BY ; X,Y=1,2,3). To our knowledge, a clear and descriptive demon-
stration of the matrix approach has been missing in the literature to date. Here,
the character table for water molecule and a hypothetical square shaped molecule is
derived in order to vividly demonstrate the matrix approach.

a)
rpodila@g.clemson.edu

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I. INTRODUCTION

Symmetry plays a very important role in spectroscopy. Raman and Infra-red (IR) active
modes may be inferred from simple symmetry operations on a given molecular system. Any
operation that leaves the molecular configuration invariant is considered to be a symmetry
operation1 . In general, all symmetry operations on a molecule constitute a group. Hence,
the rules of group theory may be used to obtain the character table, which contains the
information and nature of the vibration modes of the given molecule2 . But, ignoring the
fact that the representations form a group, one should still be able to develop the character
table simply by considering the matrix representations of all the symmetry operations. In
the following discussion, we explicitly show how matrices can effectively be used to obtain
the character table with out borrowing any help from the group theory.

II. THEORY

We consider water and a virtual square molecule to demonstrate the matrix approach.
As seen in Fig. 1, in case of the water molecule we have four symmetry operations namely,

FIG. 1. The possible symmetry operations that can be performed on a water molecule

identity (E), rotation by 180o (C2 ), vertical mirror plane (σv ) and a horizontal mirror plane
(σH ). We may express these as 3x3 matrices using cartesian coordinates as shown below.
If one uses the group theory then character table may be obtained from the aforemen-
tioned symmetry operations directly. However, in the case of the matrix approach before
obtaining the character table, we should take into account that both the hydrogen atoms are

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FIG. 2. Top panel shows the matrix elements of the symmetry opeation E, C2 , σv and , σH .
Bottom panels show water molecule with inequivalent H atom symmetry points and the extended
matrices for the symmetry operations

not equivalent points from the perspective of a symmetry operation. In order to distinguish
between the two H atoms, we assign directionality to them as shown in fig 2. It can be
clearly seen that the addition of such directionality to H atoms leaves the C2 operation in-
variant. However, the arrows in fig. 2 appear to change direction under the action of mirror
planes (σv ). The matrices of the symmetry operations shown in fig. 2 are incomplete with
out the inclusion of the directionality. This may be included into the 3x3 matrices (Fig.
2) by considering a virtual coordinate and hence extending the dimension of the symmetry

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operation by 1. We follow the same procedure in the case of a virtual sqaure molecule to
obtain the character table.

III. RESULTS AND DISCUSSION

The extended matrices in Fig. 2 are already diagonal and constitute a one dimensional
irreducible representation2 . Now, we may write the character table as in Table I.

Table I. Character table for water molecule

.
Thus, using simple matrix representations we could come up with four different 1D irre-
ducible representations and the character table with out any help from group theory and
demonstrated the equivalence of both the approaches. Similarly, in case of a virtual square
molecule one can derive the character table through the aforementioned procedure. A square
molecule has eight symmetry elements namely E, C4 , C4 3 , C2 , σD , σD ∗, σv , and σv ∗as shown
in Fig. 3. These eight operations may be classified into four classes: C2 , C4 , σD , σv . Their
matrices for these can be written as follows We see that these matrices are not readily

diagonal but block diagonal. The blocks indicated in the above matrices constitute a 2D
irreducible representation and a 1D irreducible representation. As in the previous case of

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water moleclue, we now consider the fact that the four atoms on the vertices of the square
are not the same from the perspective of a symmetry operation. If we distinguish the atoms
in the following three ways then we may extend the dimension of matrices by including 3
virtual coordinates:

FIG. 3. Symmetry operations on a virtual square molecule

FIG. 4. Extended matrices and distinguised atoms of a virtual square molecule

Now we may write the character table for a virtual square molecule from the above
matrices (Table II). We have a 2D representation given by the first block diagonal matrix

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and other diagonal elements lead to 4 individual 1D representations. The trace of this block
diagonal matrix is also called the character. We note that the trace remains invariant under
similarity transformations. Since we need only the character, we need not explicitly find
principal axes or a similarity transformation for the block diagonal matrix above.

Tabe II. Character table for a square molecule

IV. CONCLUSION

Here we have explicitly worked with matrices to come up with the character table for
water and a virtual square molecules. The matrix representations of various operations were
extended by including extra co-ordinates, which distinguish between similar atoms in the
molecules.

REFERENCES

1
D. C. Harris and M. D. Bertolucci Symmetry and Spectroscopy (Dover Publications, INC.,
NY, 1989).
2
M. S. Dresselhaus, G. Dresselaus and A. Jorioi Group Theory (Springer-Verlag Publications,
Berlin, 2008).