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DOI 10.1007/s10440-012-9675-5

Applications of Symmetry and Group Theory

for the Investigation of Molecular Vibrations

Jaan Laane Esther J. Ocola

Received: 25 April 2011 / Accepted: 16 November 2011 / Published online: 8 February 2012

Springer Science+Business Media B.V. 2012

Abstract The application of symmetry and mathematical group theory is a powerful tool for

investigating the vibrations of molecules. In this paper, we present an overview of the meth-

ods utilized. First we briey discuss the quantum mechanical nature of vibrations and the

experimental methods used. We then present the principal concepts for applying group the-

ory to molecules. The symmetry operations which are used to comprise groups are described

and then used to determine the point groups of molecules. The properties of character tables

are presented and the method for obtaining a reducible representation for all the motions of

a molecule is detailed. This can then be broken down to obtain the irreducible representa-

tion which contains the symmetry species of the individual vibrations. The determination

of symmetry adapted linear combinations is outlined and the basis for spectroscopic selec-

tion rules is presented. The paper concludes by examining how matrix algebra along with

symmetry concepts simplies calculations with molecular force constants.

Keywords Symmetry Group theory Molecular vibrations Potential energy Symmetry

adapted linear combinations Selection rules

Mathematics Subject Classication (2000) 20-01 58D19

1 Introduction

One of the notable developments in chemistry during the second half of the twentieth century

was the emergence of symmetry and group theory as a means to better understand molecular

spectroscopy, molecular bonding, and molecular reactions and dynamics. The well known

book series by Nobel laureate Gerhard Herzberg [13] published in 1945 to 1966 already

used these concepts to present the principles of molecular spectroscopy, but this was done

in a fairly complicated way. A major advance came when our late colleague F.A. Cotton

at Texas A&M University rst published his book Chemical Applications of Group Theory

J. Laane () E.J. Ocola

Department of Chemistry, Texas A&M University, College Station, TX 77843-3255, USA

e-mail: laane@mail.chem.tamu.edu

4 J. Laane, E.J. Ocola

Fig. 1 Natural symmetry of a

snowake

in 1963. The third edition [4] appeared in 1993. This text presented symmetry and group

theory in a way that the average chemist could understand. Another very good and early

book, although somewhat more advanced, was the text by Tinkham [5]. Following these,

numerous other books of varying depth have been published on this topic [620].

In the present paper we will attempt to present a condensed version of how the use of

symmetry and group theory can be applied to better understand molecular vibrations and

to simplify the calculations that are utilized for these purposes. Everyone has some kind of

conception of symmetry. Thus, when looking at the snowake in Fig. 1, it is evident that it

can be cut in half many ways leaving two identical sides. Similarly it can be rotated by 60

after which it looks just the same. These same ideas can be applied to molecules as we shall

see.

This paper is organized as follows. In Sect. 2, we present some basic concepts for the

study of molecular vibrations. In Sect. 3, we examine the applications of symmetry and

group theory to molecules. In Sect. 4, we describe the implementation of symmetry adapted

linear combinations for the representation of vibrations. Section 5 describes the origin of

spectroscopic selection rules based on symmetry, and Sect. 6 examines the effect of symme-

try on the vibrational potential energy. A brief conclusion is given in Sect. 7.

2 Molecular Vibrations

2.1 Vibrations of a Diatomic Molecule

A two-atom or diatomic molecule can have six different individual motions. It can translate

in three directions, it can rotate about two axes, or it can have a vibration where the distance

between the atoms rapidly gets larger or smaller (perhaps 10

14

times per second). There are

only two molecular rotations since one of the Cartesian axes passes through the atoms and

hence there is no moment of inertia about this axis (I =

m

i

r

2

i

where m

i

= mass of atom

and r

i

= distance from axis). Our interest is in the molecular vibration, which is generally

approximated by the harmonic oscillator model. Here, the bond is pictured to be similar to

a spring so that the potential energy function for the vibration can be written

V =

1

2

kx

2

(1)

Applications of Symmetry and Group Theory for the Investigation 5

where x = R R

e

is the bond displacement from its equilibrium position R

e

and k is a

force constant (or spring constant). Use of this potential function in the Schrdinger wave

equation

2

2

d

2

dx

2

+V =E (2)

allows the quantum energy levels E to be calculated along with their corresponding wave

functions. The constant =

h

2

where h is the well known Plancks constant, and the are

the wave functions. The reduced mass is given by

=

m

1

m

2

m

1

+m

2

(3)

where m

1

and m

2

are the masses of the two atoms in the molecule. Equation (2) can be

solved exactly to yield

E =

v +

1

2

h and

v

=N

v

H

v

(

1

2

x)e

x

2

2

(4)

where the frequency is given by

=

1

2

1

2

(5)

and the quantum number v = 0, 1, 2, . . . , N

v

is a normalization constant, H

v

is the Hermite

polynomial of degree v, and =

(k)

1

2

molecule is generally presented on a wavenumber scale in cm

1

() where

=

c

=

1

2c

1

2

(6)

and typically the v = 0 1 quantum transition is observed at this value since all of the

energy levels are calculated to have a spacing of h.

2.2 Vibrations of Water

For larger molecules the vibrational problem becomes multi-dimensional, requiring 3N 6

coordinates for an N atom non-linear molecule. Of the 3N degrees of freedom, six represent

the translations and rotations. Vibrational motions are best described by internal coordinates

such as molecular bonds and bonding angles. As an example, Fig. 2 shows the three internal

coordinates for the two-bond stretching and one-angle bending motions of water. For this

case the quadratic potential energy function is

2V = f

R

(R

1

)

2

+f

R

(R

2

)

2

+f

()

2

+2f

RR

(R

1

)(R

2

)

+2f

R

()(R

1

) +2f

R

()(R

2

), (7)

where R

1

and R

2

represent the stretching of the two bonds and where is the bend-

ing of the HOH angle. The force constants f

R

and f

stretching and bending motions, respectively, and f

RR

and f

R

are interactive constants.

The detailed methods for calculating the vibrational frequencies of polyatomic molecules

were nicely presented by Wilson, Decius, and Cross [21].

6 J. Laane, E.J. Ocola

Fig. 2 Internal coordinates of

water

Fig. 3 Infrared and Raman

transitions for a molecular

vibration

2.3 Experimental Methods

There are two primary methods for studying molecular vibrations which generally have their

quantum state separations in the 100 to 4000 cm

1

range. Figure 3 shows the possible tran-

sitions for a diatomic molecule. Infrared absorption experiments typically involve a direct

transition fromthe vibrational ground state (v = 0) to the rst excited quantumstate (v = 1).

Many commercial instruments are available and these utilize the concept of Fourier trans-

form infrared (FT-IR) spectrometry where two light beams are separated by a beam splitter

and then combined to give an intensity versus path difference data set. Fourier transform is

then used to convert this to an intensity versus wavenumber spectrum.

Raman spectroscopy utilizes a monochromatic laser such as an argon-ion laser at

514.5 nm wavelength or a frequency doubled Nd:YAG laser at 532 nm. The laser induces the

sample to produce a quasi-excited or virtual state which then scatters the radiation isotrop-

ically as either Rayleigh light or Raman radiation. The Rayleigh scattering, which has the

same frequency as the laser exciting line, is about a million times more intense than the

Raman scattering which is shifted in frequency. Raman spectra are generally collected as

Stokes scattering when molecules are excited from the lowest ground state vibrational level

and these have frequencies of

RAMAN

=

LASER

VIBRATION

(8)

so that the vibrational frequency can be determined. As will be discussed later, the selection

rules for which transitions can be observed are different for infrared and Raman spectra. As

an example of how the two types of spectra differ, Fig. 4 presents the observed spectra for

an organic molecule, 3-cyclopenten-1-one. This molecule has 30 vibrations and the bands

corresponding to many of them are shown in the gure. Note that both types of spectra are

needed in order to observe most of the vibrations.

Applications of Symmetry and Group Theory for the Investigation 7

Fig. 4 Infrared and Raman

spectra for the

3-cyclopenten-1-one molecule

Table 1 Symmetry elements and

operations for molecular systems

Element Symbol Operation

Identity E Nothing

Proper rotation axis C

n

Rotate by 360/n n = 2, 3, 4, . . .

Plane of symmetry Reection through plane

(

v

= vertical;

h

= horizontal;

d

= dihedral)

Center of inversion i Inversion though center

Improper rotation axis S

n

C

n

followed by

h

3 Applications of Symmetry and Group Theory

The principal concepts for applying mathematical group theory to chemical systems are the

following:

1. Symmetry operations performed on molecules make up the members of a mathematical

group.

2. All the properties and requirements for a mathematical group apply. This includes the

fact that the product of any two operations must also be a member of the group and

that any operation X must have an inverse such that XX

1

= E where E is the identity

operation.

3. A valid symmetry operation performed on a molecule produces a result where the

molecule appears to be identical to its original position.

4. Symmetry operations are carried out with respect to symmetry elements.

Table 1 presents a list of the symmetry elements and the corresponding symmetry opera-

tions. Examples of these will be shown for the benzene molecule (C

6

H

6

) which is a hexagon

of six carbon atoms with one hydrogen atom attached to each. Figure 5 rst shows the op-

erations about the C

6

proper rotation axis. A C

6

operation is a rotation of 60

, a C

2

6

= C

3

operation is a rotation by 120

6

6

gets you back to the original arrangement

of atoms, so this is equivalent to the identity E. Figure 6 shows the two types of C

2

rotation

axes which benzene also possesses. Note that there are a total of six C

2

axes perpendicular

to the C

6

axis and this will be the basis for the molecule having D

6h

point group symmetry.

8 J. Laane, E.J. Ocola

Fig. 5 Symmetry operations about the C

6

axis for benzene

Fig. 6 The two types of C

2

axes

for benzene which are

perpendicular to the C

6

axis

Fig. 7 The three types of

reection planes for benzene

Fig. 8 The inversion (top) and

improper rotation (bottom)

operations of benzene

Figure 7 shows three different planes of symmetry,

h

(horizontal),

v

(vertical), and

d

(dihedral). Figure 8 shows the effect of the inversion and improper rotation operations. Note

that whether the atoms wind up right side up or inverted is important. In total, benzene has

Applications of Symmetry and Group Theory for the Investigation 9

T

a

b

l

e

2

C

h

a

r

a

c

t

e

r

t

a

b

l

e

a

n

d

r

e

d

u

c

i

b

l

e

r

e

p

r

e

s

e

n

t

a

t

i

o

n

f

o

r

t

h

e

b

e

n

z

e

n

e

m

o

l

e

c

u

l

e

o

f

D

6

h

s

y

m

m

e

t

r

y

D

6

h

E

2

C

6

2

C

3

C

2

3

C

2

3

C

2

i

2

S

3

2

S

6

h

3

d

3

v

A

1

g

1

1

1

1

1

1

1

1

1

1

1

1

x

2

+

y

2

,

z

2

A

2

g

1

1

1

1

1

1

1

1

1

1

R

z

B

1

g

1

1

1

1

1

1

1

1

1

1

1

1

B

2

g

1

1

1

1

1

1

1

1

1

1

E

1

g

2

1

2

0

0

2

1

2

0

0

(

R

x

,

R

y

)

(

x

z

,

y

z

)

E

2

g

2

1

2

0

0

2

1

2

0

0

(

x

2

y

2

,

x

y

)

A

1

u

1

1

1

1

1

1

1

A

2

u

1

1

1

1

1

1

1

z

B

1

u

1

1

1

1

1

1

1

1

1

1

1

B

2

u

1

1

1

1

1

1

1

1

1

1

1

E

1

u

2

1

2

0

0

1

1

2

0

0

(

x

,

y

)

E

2

u

2

1

2

0

0

2

1

1

2

0

0

3

6

0

0

0

4

0

0

0

0

1

2

0

4

10 J. Laane, E.J. Ocola

Fig. 9 Symmetry operations for

the ammonia molecule

demonstrating the product rule

Table 3 Product table for C

3v

C

3v

E C

3

C

2

3

v

(A)

v

(B)

v

(C)

E E C

3

C

2

3

v

(A)

v

(B)

v

(C)

C

3

C

3

C

2

3

E

v

(B)

v

(C)

v

(A)

C

2

3

C

2

3

E C

3

v

(C)

v

(A)

v

(B)

v

(A)

v

(A)

v

(B)

v

(C) E C

3

C

2

3

v

(B)

v

(B)

v

(C)

v

(A) C

2

3

E C

3

v

(C)

v

(C)

v

(A)

v

(B) C

3

C

2

3

E

24 symmetry operations that can be performed, and these are shown as the heading for the

D

6h

character table in Table 2. Note that the coefcients for the operations either indicate

how many there are of the same type (3C

2

, 3C

2

, 3

d

, 3

v

) or how many can be performed

about the same axis (2C

6

=C

6

, C

5

6

; 2C

3

=C

3

, C

2

3

; 2S

6

=S

6

, S

5

6

; 2S

3

=S

3

, S

2

3

). Utilization

of character tables will be discussed later.

One of the rules for mathematical groups is that the product of any two operations is also

a member of the group. Figure 9 shows the ammonia molecule (NH

3

) which belongs to the

C

3v

point group which has two C

3

operations and three reection planes. The effect of a

C

3

operation followed by a reection through plane A is shown. It is also shown that this

product is equivalent to a reection through a different plane B. In other words C

3

v

(A) =

v

(B). Table 3 presents the product table for C

3v

symmetry. Note that each product is a

member of the group and that each has an inverse.

As can be seen, it is important to identify the symmetry point group of a molecule. Table 4

summarizes the possible point groups for molecules. Scheme 1 shows in a concise way how

to determine the appropriate point group. This scheme precludes having a molecule of S

n

symmetry which is extremely rare.

Scheme 1

1. Decide if molecule is octahedral (O

h

), tetrahedral (T

d

), or linear (D

h

with center of

symmetry; C

v

with no inversion center).

2. If not, look for highest order proper axis (C

n

). If present, go to 4.

3. If no C

n

, look for which gives a C

s

point group. If no , the molecule has C

1

or the

minimal symmetry.

4. Look for nC

2

axes perpendicular to the highest order C

n

axis. If present, go to 7.

5. Look for

h

reection plane perpendicular to C

n

. If present, the symmetry is C

nh

.

Applications of Symmetry and Group Theory for the Investigation 11

Table 4 Summary of point groups

Point group Important symmetry elements Order of the group

C

1

E 1

C

i

i 2

C

s

2

C

n

C

n

n

S

n

S

n

(very rare) n

C

nv

C

n

,

v

2n

C

nh

C

n

,

h

2n

D

n

C

n

, C

2

(very rare) 2n

D

nd

C

n

, C

2

,

d

(also S

2n

) 4n

D

nh

C

n

, C

2

,

12

4n

C

v

Linear molecules without center of inversion

D

h

Linear molecules with center of inversion

T

d

Terahedral symmetry 24

O

h

Octahedral symmetry 48

n

=C

nh

Fig. 10 Examples of molecules

with octahedral, tetrahedral, and

linear symmetries

6. If no

h

, look for n

v

planes. If present, the symmetry is C

nv

. If not, the symmetry point

group is C

n

.

7. Look for

h

. If present, the symmetry is D

nh

.

8. If no

h

, look for n dihedral planes bisecting C

2

axes. If present, the symmetry is D

nd

. If

not, it is D

n

.

Figure 10 shows O

h

, T

d

, D

h

, and C

v

molecules and lists some of their operations.

Figures 11 and 12 show C

2v

, C

3v

, D

3h

, and D

2h

molecules along with the steps which lead

to their identication.

We now turn to the use of character tables. Based on Schurs lemma in the representation

theory of nite groups [22, 23], matrix elements of irreducible representations of a nite

group satisfy certain orthogonality relations. Here the great orthogonality theorem applies.

As given by Nowick [24] it can be stated as follows:

Theorem 1 (The Great Orthogonality Theorem [24]) Express the th irrep of a group by

the set of matrices [D

()

(R)]

ij

where R is one of the operations of the group G, and take the

12 J. Laane, E.J. Ocola

Fig. 11 Examples of C

2v

and C

3v

molecules

Fig. 12 Examples of D

3h

and D

2h

molecules

dimensionality of this irrep to be l

obey the equation

R

[D

()

(R)]

ij

[D

()

(R)]

pq

=(h/l

ip

jq

where denotes the complex conjugate, h is the order of the group G and the s are all

Kronecker s.

This rather complicated equation may be interpreted as follows. The fact that the order

of the group is h means that each irrep has h matrices. Suppose we treat the corresponding

elements of these matrices, for example [D

()

(R)]

ij

for given i and j, as we vary the group

operation R, as a vector in h-dimensional space. There are l

2

l

2

l

2

in all. All members of this collection of h vectors are orthogonal to each other (dened so

that complex conjugates are used in the dot products, where necessary). Further it tells us

that the magnitude of each other vector (the dot product with itself) equals h/l

.

Applications of Symmetry and Group Theory for the Investigation 13

Fig. 13 Effect of a C

2

operation

on the translational motions of

water

Table 5 The character table for the C

2v

symmetry point group. The reducible representation for water is

also given

C

2v

E C

2

v

(xz)

v

(yz)

A

1

1 1 1 1 z x

2

, y

2

, z

2

A

2

1 1 1 1 Rz xy

B

1

1 1 1 1 x, Ry xz

B

2

1 1 1 1 y, Rx yz

9 1 3 1

Next we turn to the characters

()

(R) of the various irrep matrices. From the denition

of the character, it readily follows that the characters obey their own orthogonality relation

()

(R)

()

(R) =h

Again, we may think of the characters of each irrep as forming an h-dimensional vector.

These vectors are all orthogonal to each other and that the magnitude of each is equal to h,

the order of the group.

The sum of the diagonal elements of a matrix representation is called a character. The

number of irreducible representations of a nite group is equal to the number of conjugacy

classes of that group. Each character takes a constant value on a conjugacy class. We will

use the water molecule (Figs. 2 and 13) of C

2v

symmetry as an example. Table 5 shows

the character table for any C

2v

molecule which has C

2

,

v

, and

v

operations in addition

to the identity. The character table lists four symmetry species and each has either a +1 or

1 value for the operations shown. A positive value means that the motion (or orbital) of

interest is symmetric with respect to that operation while a 1 means it is antisymmetric.

This is readily understood if we examine the translational and rotational motions of water.

Figure 13 shows the effect of a C

2

operation on the three translational motions. The C

2

axis is taken to be the z direction and the molecule is in the xz plane. It is evident that the

C

2

operation will leave the direction of T

z

unchanged, but the vectors of T

x

and T

y

change

direction. Hence, we can place a +1 character under C

2

for the T

z

operation while T

x

and

14 J. Laane, E.J. Ocola

Table 6 Characters for molecular motions of water

C

2v

E C

2

v

(xz)

v

(yz)

T

z

1 1 1 1 A

1

T

x

1 1 1 1 B

1

T

y

1 1 1 1 B

2

R

z

1 1 1 1 A

2

Vibrations:

Symmetric stretch 1 1 1 1 A

1

Antisymmetric stretch 1 1 1 1 B

1

Bend 1 1 1 1 A

1

Fig. 14 Effect of C

2

and

v

operations on a rotation of the

water molecule

Fig. 15 The three vibrations of

water: symmetric stretching

(A

1

), antisymmetric stretching

(B

1

), and angle bending (A

1

),

respectively

T

y

have 1 characters. The

v

(xz) reection leaves T

z

and T

x

in the same direction (+1

characters) while T

y

switches direction. Similarly

v

(yz) leaves T

z

and T

y

in their original

direction but the direction of T

x

is changed. Table 6 summarizes these results and shows that

the T

z

, T

x

, and T

y

characters match symmetry species A

1

, B

1

, and B

2

, respectively. Note

that in Table 5 this fact is already identied by the location of the x, y, and z to the right of

the character table. Figure 14 shows the effect of the C

2

and

v

operations on the rotation

about the z axis and Table 6 presents the characters for each of the operations. These show

R

z

to be of symmetry species A

2

, and Table 5 can be seen to identify each of the rotational

symmetries.

When a vibrational description is known, we can use this + or method to also deter-

mine the symmetry species for vibrations. Figure 15 shows the three vibrations of water. The

behavior of each motion (symmetric or antisymmetric) upon each operation is also summa-

Applications of Symmetry and Group Theory for the Investigation 15

Fig. 16 The effect of a C

4

operation on the Cartesian

coordinates of PtCl

2

4

rized in Table 6. For example, the antisymmetric stretch is antisymmetric with respect to the

C

2

and

v

(yz) operations, but symmetric to reection in the

v

(xz) plane and thus has B

1

symmetry. The other two vibrations have A

1

symmetry species.

We now address how symmetry operations are represented mathematically. Figure 16

shows the Pt Cl

2

4

molecular ion of D

4h

symmetry. The fteen Cartesian coordinate vectors

needed to represent all the motions for the ve atoms are also shown, and the effect of a C

4

operation on the positions of all these vectors is presented. A matrix for the C

4

operation

can be used to transform a column matrix of the original coordinates to the new coordinate

positions, and this is shown below.

0 0 0 0 1 0 0 0 0 0 0 0 0 0 0

0 0 0 1 0 0 0 0 0 0 0 0 0 0 0

0 0 0 0 0 1 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 1 0 0 0 0 0 0 0

0 0 0 0 0 0 1 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 1 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 1 0 0 0 0

0 0 0 0 0 0 0 0 0 1 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 1 0 0 0

0 1 0 0 0 0 0 0 0 0 0 0 0 0 0

1 0 0 0 0 0 0 0 0 0 0 0 0 0 0

0 0 1 0 0 0 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 0 0 1 0

0 0 0 0 0 0 0 0 0 0 0 0 1 0 0

0 0 0 0 0 0 0 0 0 0 0 0 0 0 1

x

1

y

1

z

1

x

2

y

2

z

2

x

3

y

3

z

3

x

4

y

4

z

4

x

5

y

5

z

5

y

2

x

2

z

2

y

3

x

3

z

3

y

4

x

4

z

4

y

1

x

1

z

1

y

5

x

5

z

5

(9)

This shows that x

1

is moved to where y

2

was previously, y

1

goes to x

2

, and so on as

a result of the C

4

operation. Fortunately, it is only necessary to have the character or trace

(sum of the diagonal elements) of the C

4

matrix in order to analyze molecular motions. Note

that for PtCl

2

4

the character for the C

4

operation is +1 and this arises from the fact that the

z

5

vector on the Pt atom has not moved. In all cases, contributions to the character only

come from unshifted atoms when an operation is performed. Although vectors x

5

and y

5

are

also on the Pt atom, these do not contribute to the character since they are turned 90

from

their original direction. What simplies matters a great deal is that each type of operation

produces the same contribution to the character per unshifted atom. For a C

4

operation this

is always +1 since one vector goes into itself and the other two do not contribute. Figure 17

shows the effect of E, , and C

2

operations on any unshifted atom and why they contribute

+3, +1, and 1, respectively, to the character. Table 7 shows the contribution per unshifted

atom for all types of the operations.

We will now apply this approach to the motions of water using Table 5. For the C

2

and

(yz) operations only the oxygen atom is unshifted while all three atoms are unshifted

16 J. Laane, E.J. Ocola

Fig. 17 Effect of E, , and C

2

operations on the Cartesian

coordinates of an unshifted atom

Table 7 Contribution per unshifted atom (for atom vectors)

Operation Contribution Operation Contribution

E 3 (any) 1

C

2

1 i 3

C

3

0 S

3

2

C

4

1 S

4

1

C

5

1 +2cos(72

) S

5

1 +2cos(72

)

C

6

2 S

6

0

C

L

1 +2cos(360

/L) S

L

1 +2cos(360

/L)

for the (xz) reection. Utilizing the contribution per unshifted atom information in Table 7

then results in the reducible representation in Table 5. This can then be broken down to an

irreducible representation consisting of the symmetry species as components. The following

formula is used:

n

1

g

j

g

j

x

j

x

j

g

, (10)

where

= particular symmetry species such as A

1

or A

2

,

n

g =

g

j

= total number of symmetry operations (add coefcients in heading),

g

j

= number of operations in class j (coefcient for particular column);

this is often one (implied),

x

j

= number in character table for species for operation class j;

this is +1 or 1 for non-degenerate species,

x

j

g

= character in reducible representation for operation j.

Applications of Symmetry and Group Theory for the Investigation 17

As an example, to calculate how many of the A

2

symmetry species are in , we see that

each g

j

is one and g = 4. Then

n

A

2

=

1

4

[1 1 9 +1 1 1 +1 1 3 +1 1 1] = 1. (11)

The total result is that the 3N = 9 motions of water can be described as

= 3A

1

+A

2

+3B

1

+2B

2

. (12)

Table 5 shows the symmetry species for the translations and rotations are

TRANS

=A

1

+B

1

+B

2

. (13)

and

ROT

=A

2

+B

1

+B

2

. (14)

When these are subtracted from above, we are left with the symmetry species for the

vibrations as

VIB

=

TRANS

ROT

= 2A

1

+B

1

. (15)

These vibrations were shown in Fig. 15.

We will now apply this approach to the 12 atom benzene molecule using Table 2 where

the reducible representation is also shown. results from examining the number of un-

shifted atoms for each operation and then using Table 7 to get the total contribution. The

result for the 36 motions of benzene is

=2A

1g

+2A

2g

+2B

2g

+2E

1g

+4E

2g

+2A

2u

+2B

1u

+2B

2u

+4E

1u

+2E

2u

. (16)

Note that E type symmetry species represent two motions. Table 2 shows the translations

to be of symmetry A

2u

+E

1u

and rotations to be A

2g

+E

1g

. Thus the symmetry species for

the 30 vibrations of benzene are

VIB

=

TRANS

ROT

= 2A

1g

+A

2g

+2B

2g

+E

1g

+4E

2g

+A

2u

+2B

1u

+2B

2u

+3E

1u

+2E

2u

. (17)

Previously in Fig. 4 we presented the spectra of an organic molecule of C

2v

symmetry.

When symmetry considerations are applied here, we nd the vibrational symmetry species

are

VIB

= 10A

1

+5A

2

+9B

1

+6B

2

. (18)

When the vibrations are numbered, as they are in Fig. 4, we start with the rst symmetry

species and label the vibrations from highest frequency down. The rst vibration (

1

) is

then the highest frequency A

1

mode which happens to be a CH bond stretching vibration

with frequency 3079 cm

1

. Vibration

10

is a bending motion of the ve-membered ring

of A

1

symmetry at 623 cm

1

. The next vibration numbered is

11

which is the highest

frequency vibration with A

2

symmetry and so on. The last numbered vibration

30

is the

lowest frequency B

2

motion at 83 cm

1

.

18 J. Laane, E.J. Ocola

4 Symmetry Adapted Linear Combinations (SALCs)

In our discussion of water we pointed out that vibrations are best represented by internal

coordinates as shown in Fig. 2. We now show how the application of symmetry enables us to

provide better descriptive pictures of the vibrations. During a molecular vibration equivalent

bonds or angles stretch or bend simultaneously, but not necessarily in the same direction.

Thus, for water, the two oxygen-hydrogen molecular bonds R

1

and R

2

will either stretch

at the same time or one will stretch while the other contracts. This is shown in Fig. 15.

The method of symmetry adapted linear combinations (SALCs) allows us to calculate how

equivalent internal coordinates combine. The formula is

S

Op

Op

Op(In

1

), (19)

where S

Op

is the value in the character table

for species and operation Op, and Op(In

1

) is the resulting internal coordinate when the

operation Op is performed on the initial internal coordinate of choice In

1

, and is the

normalization constant. This process is shown below when the bond stretching coordinate

R

1

of water is selected as In

1

:

C

2v

E C

2

v

(xz)

v

(yz)

Op(R

1

) R

1

R

2

R

1

R

2

(20)

Thus R

1

stays in its own position upon E and

v

(xz) operations but moves to where R

2

was

upon C

2

and

v

(yz) operations. The result above in combination with (19) yields

S

A

1

= (2R

1

+2R

2

), (21)

S

B

1

= (2R

1

2R

2

), (22)

and

S

A

2

=S

B

2

=0. (23)

The normalization condition requires that

c

2

i

= 1, (24)

where the c

i

are the coefcients for the internal coordinates. Thus, (21) and (22) become

S

A

1

1

=2

1

2

(R

1

+R

2

) (25)

and

S

B

1

3

=2

1

2

(R

1

R

2

) (26)

The have been inserted to indicate the vibrations actually involve the change in the bond

distances R

1

and R

2

. The B

1

SALC is labeled as S

3

since

S

A

1

2

= (27)

is numbered rst since it belongs to A

1

symmetry. In this case, there is only one angle to

bend and has nothing to combine with so the SALC is the same as the internal coordinate.

Applications of Symmetry and Group Theory for the Investigation 19

Fig. 18 The effect of symmetry

operations on the internal

coordinates of ethylene

Fig. 19 SALCs representing the CH bond stretching and angle bending vibrations of ethylene

To further demonstrate SALCs we examine the CH bond stretching and HCH angle

bending internal coordinates of ethylene shown in Fig. 18. The effect of each operation is

shown. When used together with a D

2h

character table, the SALCs shown in Fig. 19 result.

For this molecule and in many cases, the SALCs shown are actually very good representa-

tions for the so-called normal coordinates which are the precise descriptions of the vibra-

tional motions. Mixing or vibrational coupling of motions of the same symmetry species

is allowed, but no interactions between different symmetry species may occur.

5 Spectroscopic Selection Rules

The vibrational spectra of molecules involve transitions between quantum states and these

were shown for infrared absorption and Raman scattering transitions in Fig. 3. For an in-

frared transition to occur the molecule must have a change in dipole moment (a change

20 J. Laane, E.J. Ocola

in charge distribution) during the vibration, and this can be determined by symmetry con-

siderations. Namely, the following transition moment integral R

if

must not be zero for an

allowed transition:

R

if

=

f

M

i

d = f ||i. (28)

The expression on the right is in the more concise Dirac notation. Here,

i

and

f

are

the wave functions for the initial and nal states of the transition, and

f

is the complex

conjugate of

f

. Also here M

x, y, or z) in terms of the vibrational coordinate Q:

M

=M

0

0

Q+

2

M

Q

2

0

Q

2

+ . (29)

Then

f ||i =M

0

f |i +

2

M

Q

2

0

f |Q|i + . (30)

The rst term is zero due to the fact that the wave functions are orthogonal. It can readily

be shown that R

if

is non-zero only if the direct product of the symmetries of

i

, Q, and

f

is totally symmetric where all the characters for the symmetry species are +1 (A

1

for

C

2v

symmetry, for example). For vibrations the initial state is totally symmetric and the

symmetry species for Q is the same as T

x

, T

y

, or T

z

. Thus for R

if

to be non-zero,

f

must have the same symmetry species as T

x

, T

y

, or T

z

. This is because the direct product

of a symmetry species times itself is totally symmetric (e.g., B

1

B

1

= A

1

for C

2v

). This

provides a simple way to identify infrared active vibrations since they are those that have an

x, y, z at the right hand side of a character table. For C

2v

these are A

1

, B

1

, and B

2

. For D

6h

they are A

2u

and E

1u

.

For Raman transitions the polarizability of a molecule must change during a vibration.

This essentially means that the shape of the molecule must change. This is generally true

for more symmetric vibrations but often not true for antisymmetric motions such as the

antisymmetric CO bond stretching of carbon dioxide. Mathematically, the product of two

integrals must be non-zero:

P

if

= f ||jj||i, (31)

where i and f are the initial and nal states and j is the virtual state shown in Fig. 3.

For the second integral to be non-zero j must have the same symmetry as since i is

totally symmetric. Then in the rst integral the direct product of and j must match that

of the vibrational level f . Hence, the vibration must have the same symmetry as the tensor

element to be Raman active. Each character table lists these at the right side of the

table. For C

2v

all of the symmetry species correspond to Raman active vibrations. For D

2h

symmetry only the A

1g

, E

1g

, and E

2g

vibrations are Raman active. In Raman experiments

different vibrations can also be determined to be either Raman polarized or depolarized

depending on how the intensities vary with laser beam polarization. As it turns out, only the

totally symmetric vibrations have polarized Raman bands. There are also other spectroscopic

processes such as two-photon absorption and hyper Raman for which the selection rules can

be determined in a similar way.

To demonstrate the application of selection rules we will examine the predicted spectral

features of two organic molecules with the same formula but belonging to different symme-

try point groups. The cis- and trans-dichloroethylene molecules of C

2v

and C

2h

symmetry,

Applications of Symmetry and Group Theory for the Investigation 21

Fig. 20 Cis- and

trans-dichloroethylene molecules

Table 8 Infrared and Raman bands expected for isomers of 1,2-dichloroethylene

Isomer Symmetry Raman bands Raman polarized Infrared bands

cis C

2v

12 5 10

trans C

2h

6 5 6

respectively, are shown in Fig. 20. The cis molecule has vibrations

cis

(C

2

) = 5A

1

+2A

2

+4B

1

+B

2

, (32)

IR, R(P) R IR,R IR,R

while the trans has

trans

(C

2h

) = 5A

g

+B

g

+2A

u

+4B

u

. (33)

R(P) R IR IR

For each symmetry species, the infrared (IR) and/or Raman (R) activity are shown and

the polarized Raman bands [R(P)] are also indicated. Table 8 summarizes the number of

bands expected for the infrared and Raman spectra. As can be seen, the two molecules are

easy to distinguish based on symmetry selection rules. The experimental spectra for these

molecules can be found elsewhere [25].

6 Effect of Symmetry on Potential Energy

We now wish to show how symmetry helps to simplify the computation of vibrational fre-

quencies and force constants. We will use the water molecule with its internal coordinates

shown in Fig. 2 as an example. First we note that the internal coordinates can be represented

by a column matrix R which is dened by a transformation from Cartesian coordinates X:

R =BX. (34)

For water X is a column matrix of the nine Cartesian coordinates required to dene the

positions of the three atoms. B is the 3 9 transformation matrix which will not be shown

here. For water,

R =

R

1

R

2

. (35)

22 J. Laane, E.J. Ocola

These internal coordinates can be transformed to symmetry coordinates using

S =UR, (36)

where for water

S =

S

1

S

2

S

3

(37)

is based on the denitions in (25)(27) so that

U=

1

2

2

1

2

0

0 0 1

2

1

2

2

1

2

0

. (38)

The potential energy is given by

2V = R

FR. (39)

For water the potential function in terms of internal coordinates is given in (7) so that

F =

f

R

f

RR

f

R

f

RR

f

R

f

R

f

R

f

R

f

. (40)

This can be converted to a symmetric set of force constants using the similarity transforma-

tion

F

sym

= UFU

. (41)

For water this becomes

F

sym

=

F

11

F

12

0

F

21

F

22

0

0 0 F

33

(f

R

+f

RR

) 2

1

2

f

R

0

2

1

2

f

R

f

0

0 0 (f

R

f

RR

)

. (42)

Then in terms of symmetry coordinates we have

2V = S

F

sym

S. (43)

The solution of the vibrational problem also requires the consideration of the kinetic energy

which can be written as

2T = R

G

1

R. (44)

where G

1

is the reciprocal of the G matrix which is determined from the geometry of the

molecule and the masses of the individual atoms. Details for its calculation can be found

elsewhere [21]. The same symmetry considerations apply to the G matrix as they do for F.

Namely

G

sym

= UGU

. (45)

Applications of Symmetry and Group Theory for the Investigation 23

Once the F and G matrices are available, the vibrational eigenvalues can be calculated and

then related to the vibrational frequencies :

=4

2

2

. (46)

In internal coordinates,

|GF E| =0, (47)

where E is the identity matrix. For water this would be a 3 3 determinant that needs

to be solved (or matrix diagonalization methods can be used). However, use of symmetry

coordinates results in

|G

sym

F

sym

E| = 0, (48)

and the resulting determinant can be broken up in terms of the individual symmetry species.

For water a 22 determinant for A

1

results and a simple 11 determinant for the B

1

block.

For larger molecules this symmetry factoring is even more signicant. For example, for

benzene and its vibrations given in (17), instead of having a 30 30 matrix or determinant

to deal with, symmetry factoring results in ten separate symmetry blocks with the largest

being a 4 4 matrix.

7 Conclusions

In this paper we have tried to convey how powerful the application of symmetry and group

theory is to the analysis of molecular vibrations. However, we have only touched the surface

as the understanding of electronic and rotational spectroscopies is also greatly facilitated by

similar methods. We have also not delved deeply into demonstrating how the computation

of vibrational frequencies and force constants is simplied to a great extent by symmetry

considerations. Symmetry and group theory are also invaluable for understanding molecular

bonding based on molecular orbital theory where molecular orbitals are generated from the

linear combination of atomic orbitals (MO-LCAO theory).

Acknowledgements The authors wish to thank the Robert A. Welch Foundation (Grant A-0396) for nan-

cial support. Yi-Ching Wang assisted with adapting the manuscript to LaTeX format.

References

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Molecules. Van Nostrand, Princeton (1945)

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trand, Princeton (1950)

3. Herzberg, G.: Molecular Spectra and Molecular Structure: III. Electronic Spectra and Electronic Struc-

ture of Polyatomic Molecules. Van Nostrand Reinhold, New York (1966)

4. Cotton, F.A.: Chemical Applications of Group Theory, 3rd edn. Wiley, New York (1990)

5. Tinkham, M.: Group Theory and Quantum Mechanics. McGraw-Hill, New York (1964)

6. Kettle, S.F.A.: Symmetry and Structure: Readable Group Theory for Chemists, 3rd edn. Wiley, Sussex

(2007)

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24 J. Laane, E.J. Ocola

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New York (1962)

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