ORNL/TM-5666

The Use of Group Theory

in the Interpretation
of infrared and Raman Spectra

E. Silberman
H. W. Morgan

OAK RIDGE NATIONAL LABORATORY

BU
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 0RNL/TM-S666

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Physics Division

THE USE OF GROUP THEORY IN THE INTERPRETATION

OF INFRARED AND RAMAN SPECTRA

E. Silbernan
H. W. Morgan

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Date Published: January 1977 «• IMMAiMM «Mi» «»»•*• MHWtm. **
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Prepared by the
OAK RIDGE NATIONAL LABORATORY
Oak Ridge, Tennessee 37830
operated by
UNION CARBIDE CORPORATION
for the
ENERGY RESEARCH AND DEVELOPMENT ADMINISTRATION
 CONTENTS
ABSTRACT v
1. INTRODUCTION 1
2. TOE POINT GROUPS I
3. GROUPS, REPRESENTATIONS, CHARACTER TABLES, AND THE
REDUCTION FORMULA 7
4. TOE CHARACTER TABLES OF THE POINT GROUPS 8
5. GROUP THEORY AND MOLECULAR VIBRATIONS 21
6. THE PREDICTION OF THE FUNDAMENTAL VIBRATIONAL BANDS 22
7. EXAMPLES 24
7.1 Anoonia (NH 3 ) 24
7.2 Monodeuterated Ammonia (NH2D) 26
7.3 1,2-Dichloroethylene (c£a) (e-ClHC-CClH) 27
7.4 1,2-Dichloroethylene (trans) (t-ClHC*CClH) 28
7.5 Ethylene (C 2 H^) 30
7.6 Phosphorus Pentafluoride (PF S ) 32
7.7 Carbon Tetrachloride (CC1»,> 34
BIBLIOGRAPHY 37

iii
 ABSTRACT
Application of the mathematical theory of groups to the
symmetry of molecules is a powerful method which permits the
prediction, classification, and qualitative description of
many molecular properties. In the particular case of vibra-
tional molecular spectroscopy, applications of group theory
lead to simple methods for the prediction of the number of
bands to be found in th-> infrared and Raman spectra, thei-
shape and polarization, and the qualitative description of
the normal modes with which they are associated. This report
contains the tables necessary for the application of group
theory to vibrational spectroscopy and instructions on how to
use them for Molecular gases, liquids, and solutions. A brief
introduction to the concepts, definitions, nomenclature, and
formulae is also included.

v
 THE USE OF GROUP THEORY IN THE INTERPRETATION
OF INFRARED AND RAMAN SPECTRA

1. INTRODUCTION

Application of the mathematical theory of groups to the symmetry of

molecules is a powerful method which permits the prediction, classifi-
cation, and qualitative description of many molecular properties. Most
of this information would be unobtainable from first principles because
of th<; difficulties in solving the complicated equations, and, in most
cases, very long calculations would be necessary in order to obtain
equivalent information by other methods.
In the particular case of vibrational molecular spectroscopy,
applications of group theory lead to simple methods for the prediction
of the number of bands to be found in the infrared and Raman spectra,
their shape and polarization, and the qualitative description of the
normal modes with which they are associated.
This summary will include the tables necessary for the application
of group theory to vibrational spectroscopy and instructions on how to
use them for molecular g&ses, liquids, and solutions. A brief intro-
duction to the concepts, definitions, nomenclature, and formulae will be
presented, but no theoretical justification of the methods will be
given. More complete descriptions of the theory underlying such methods,
as well as their extensions to molecular solids and polymers, can be
found, at different levels of difficulty, in the annotated bibliography
included at the end of this section.

2. THE POINT GROUPS

The movement of a molecule from one position to another that is

indistinguishable from the original one (because every atom has been
replaced by another of the same kind or has not moved at all) is called
a symmetry operation. Each symmetry operation has to be carried out
with respect to a geometrical entity (point, line, or plane) which is
called a symmetry element. There are a limited number of possible

1
BLANK PAGE
 2

symmetry operations; they are listed in Table 1, together with their

usual symbols and associated symmetry elements. The identity, a trivial
symmetry which all molecules have, has been included because it has to
be taken into account in the calculations that follow. The axis of
symmetry of the highest order (if it exists) is called "principal axis,"
and it is customarily considered to be vertical; if a coordinate system
is used, the principal axis should coincide with the z axis.

Table 1. Symmetry operations

Symbol Operation Description
J Identity Rotation by 360°
C
p
p-Fold rotation Rotation by angle 2n/p
a Reflection Reflection by a plane
5
Rotation-reflection Rotation by angle 2n/p followed by
P reflection
i Inversion "Reflection" of each point through
the origin, or center of mass

A molecule may have one or more symmetry elements. Not all com-
binations of symmetry elements are possible; on the other hand, the
presence of certain pairs of symmetry elements implies the existence of
certain others. Each set of compatible symmetry operations is called a
"point group" because (1) no symmetry operation can mov<i the point
coincident with the center of mass (which is unique and cannot, therefore,
be shifted to an "equivalent" position), and (2) each set must satisfy
the conditions to constitute a mathematical "group."
Because very few known molecules have symmetry axes of order greater
than six (except «>), the number of point groups of practical interest is
limited. Table 2 lists those groups and gives typical examples of
molecules that have the corresponding symmetry in their equilibrium
configuration. Some point groups for which examples are not known are
listed because of the possibility of having to deal with molecules that
belong to them in a perturbed configuration (as may happen in liquids)
or in excited states.
 Table 2. The symmetry elements of the point groups of interest to molecular spectroscopy

Point group*2 Symmetry elements b'a Examples

Ci E CHFClBr, CH 3 'CHO
c2 c2 M2O2 (nonplanar)
c%
Cu Cu CJ(c. Cu)d
C*2(c. C 6 ) . C 3 (c.
^ (BS2) V trans-C1BrHC•CHBrC1
^(C. SU)
Se C3(c. s6), i
a N0C1 (nonlinear), NH 2 D,
C 2 H 5 C1
°2' % H2O, H 2 CCl2» chlorobenzene
NH 3 , MCCI 3 , 0PC1 3
2o«(p. av), Cj(c. Ck) IF 5 , Fe(CO) 5
3
%
3o* (b. o y ) / Ci(c. C 6 ),
C 3 (c. C G )
c to', ooqV Any Cp{c. C J HC1, HCN, HCCCl
C
°h
i fcrane-ClHC=CHCl, C 3 0 2
zh
c
°h
H 3 B0 3 , C*(NH 2 ) 3
3*
%

<? (C
V °h 2 ' V ' C3(C' C * ) f
5 6 (C. C 6 ), 5 3 (C. i
 Table 2 (continued)

Point group Symmetry elementsbtc Examples

D2=V C
2> (P» '"'2) C2(p. C2C2)
3C2(p. C 3 )
2C?2Cp• £«»» m.p.)^ 2(7^(b. CI), C*2(c. C O
C 6 , 3C 2 (p. C 6 ) 3C 2 (b. CZ.), C 2 (c. C 6 ),
C 3 (c. <76)
C 2 » 2C'(p. C 2 , m.p.)» 5„(c. C 2 ) B 2 CI k*, H2C_H
3 2'
, NU S
<•

'3 d
3C 2 (p. C 3 ), 30^ S 6 Cc. c 3 ), i C 2 H 6 , C 6 H 1 2 (cyclohexane),
(SiH 3 ) 2 0
<V 4C (
2 P- 4a
d
<?!J(c. C^), S 8 Cc. C„) S
8

°2h <SV C2' ^P* » p. C C \ ) , o'(t. C 2 C 2 ), C2Hi», p-dichlorobenzene,

o(t. C'CJ) o " ( t . C2(f'7)* i naphtalene
'3 h C 3 , 3C2(p. C 3 ), a h 5 3 (c. C 3 ), 3o y BF 3 , 1,3,5-C 6 H 3 C1 3
PtC1 2
\h Ck, 2Cz(p. CJ, <W ,'
2^'(p. C„), o h 2oy, 2(Jj, i
C s , S£72(p. C 5 ), o^ 5 (c. C 5 ), So v Cyclopentane (plane and
5k symmetric), ferrocene
eclipsed)
D
6h
C 6 , 3C z (p. C 6 ), C g H g (benzene)
S 3 (c. S 6 (c. C 6 ) ;
3oy,
 Table 2 (continued)

Point group a Symmetry elements^' 0 Examples

^ mfi
h Any cp[c. CJ, any o2, co2, c 2 h 2

Sp(.c. CJ, »oy, i

T 4C 3 , 3C 2 (m.p., b. C 3 's)
T
d
4C 3 , 3C 2 (m.p., b. C 3 's), ch 4 , w j , n h j , SO^"
s s ^ c . Cz),
6orf(t. C 3 's)
T
h
4Cy 3C2(m.p.), i 3o(t. C 2 's), 4S g (c. C3>s)
0 ^ ( m . p . ) , 4C 3 3c2(C. CJ, 6C 2
(m.p.), 4C 3 (cube 6C 2 (t. centers
3 C 2 ( c . CJ, SF6, Ptci62-, UF6
diagonals), i opposite cube edges),
3SJc. CJ, 4S g (c. CJ,
3a^(p. CJ, 6ad(t. oppo-
site cube edges)
a
In the Zu C.hV,, and C.DV, groups, aV should (if possible) pass through more atoms than o\V (which is
sometimes labeled o-,
a
in C and C©v); if the rule is not applicable, oy should intersect more bonds
than Oy. Similar rules should be used to label C2, C'2, and in groups D 2 and D ^ , and C2 and C^
in groups D k , D g , D z d , D ^ , and D ^ .
The element E (identity), which is contained in every point group, has been omitted.
c
Axes and planes pr<?c?ded by a number are equivalent (can be transformed one into the other by another
symmetry operation).
d J"F h
c. = coincident with. b. = bisecting. t. = through.
e
p. = perpendicular to. ^m.p. = mutually perpendicular.
 6

A few remarks may facilitate the use of Table 2:

1. The first column gives the name of the group in the Schoenflies
notation habitually used by molecular spectroscopists; the corresponding
notation in the Hermann and Mauguin system used in crystallography, and
more recently in solid state spectroscopy, can be found in most of the
tables given in the bibliography. Although it is not necessary to
memorize the symbols and symmetry elements of the point groups, it can
be useful to notice that: (a) the groups C a n d contain essentially
only the corresponding axis, the special cases being C1 (which really
does not have any symmetry) and C. (which has only a center of symmetry
equivalent to the operation S2); (b) the groups and C ^ are generated
by adding a a or a- plane to the groups C, the special case being C ,
v n, p ©
whose plane of symmetry can equally well be considered horizontal or
vertical, justifying the equivalent names C and (c) the dihedral
groups Dp are generated by adding a C 2 perpendicular to the principal
axis of a group C' ; the operations with both axes generate new ^ ' s
perpendicular to the C ; (d) the addition of vertical planes o^ bisecting
adjacent C 2 ' s of each D^ group gives origin to the D g groups; (e) the
addition of a horizontal plane cr^ to each D group gives origin to the
D
ph S rou P s » anci a11
above mentioned groups are called axial
point groups and can be characterized as not having more than one (if
any) axis of order three or higher. Groups that have more than one
three-fold or four-fold axis are called cubic point groups, and only two
of them are likely to be found in free molecules — T w h i c h has the
symmetry of a regular tetrahedron, and of which the cube and the
regular octahedron are the typical examples. The cubic groups T, T^,
and 0 have been included because of their usefulness in the study of the
spectra of many crystals.
2. The symmetry elements that constitute each point group have
been separated into two columns to facilitate the search when trying to
assign symmetry to a molecule. The first column lists the minimum set
that characterizes the group and, in most cases, justifies its symbol.
The second column contains symmetry elements that are a consequence of
the presence of the former ones. All the elements are equally important
 7

for the deduction of the molecular properties derived from the molecular
symmetry.
3. The table contains the 32 "crystallographic" point groups from
which the 230 crystal space groups can be derived by addition of new
elements of symmetry (translations, screw axes, glide planes). The
reader must be reminded that the methods for the interpretation of
crystal spectra are more complicated than the methods applicable only to
isolated molecules that will be described. A first approximation to the
spectra of molecular crystals can be obtained, however, by treating each
molecule or ion in the crystal as isolated, but with its own symmetry
reduced to the symmetry of the crystal at the "site" where the molecule
or ion is located.

3. GROUPS, REPRESENTATIONS, CHARACTER TABLES,

AND THE REDUCTION FORMULA

A set of elements A, B, C, ... that can be combined in pairs

according to a certain rule is said to constitute a group if (I) each
binary combination yields an element of the set, (2) the associative law
holds for the combination of more than two elements, (3) the set contains
an identity element fits combination with all the other elements leaves
them unchanged), and (4) each element has an inverse in the set (their
combination yields the identity). The combination is usually called
"product" although it does not need to be a product in the ordinary
algebraic sense and, in general, will not be commutative. It may be
useful to tabulate all the binary products in a "multiplication table."
The elements of a group may have any degree of complexity or
abstractness, and the operations necessary to obtain their products may
be very complicated. Usually it is possible to establish a correspon-
dence between each element of a group and a number or a matrix belonging
to another group ixv such a way that the multiplication tables of both
groups are "parallel." The group of numbers or matrices is called a
representation of the original group and its dimension is equal to the
order of the square matrices that constitute it (the dimension is 1 if
its elements are numbers). Many properties of a group can be found by
 8

operating with their representations, which may vary in number and

dimensions. Frequently, mathematical operations may be performed that
will factorize the matrices of a high-order representation into matrices
of lower orders, which constitute representations of lower dimensions.
When that process is carried out in such a way that the lower order
matrices cannot be further factorized, it is said that the higher order
reducible representation has been reduced to its irreducible represen-
tations. It can be proven that there are only a limited number of
irreducible representations of any group; they can, therefore, be found
and tabulated. For many applications of group theory it is enough to
know the character (sum of diagonal elements) of the representations, a
fact which explains the interest in the availability of tables of char-
acters of the irreducible representations of the point groups.
The reduction of a reducible representation to its irreducible
components may be a complicated process, but there is a simple reduction
formula which gives the number of times each irreducible representation
will appear when the reduction process is completed. If the g elements
of a group have characters x*% = 1> 2, 3, ..., g) ir». some reducible
y
representation and characters x„- (> = 1, 2, 3, ..., g) in the irreducible
v
representation q3 the reduction of the former will contain the latter N
times, with
9
y
N = - £ x^x • •
* i-1 * *

4. THE CHARACTER TABLES OF THE POINT GROUPS

The symmetry operations of the point can be described by the

equations that relate the coordinates of each atom before and after each
operation. The coefficients of these equations may be arranged in
matrices that represent the symmetry operations. The dimension of these
reducible representations will depend on the choice of a coordinate
system. If cartesian coordinates are used, each atom will require three
coordinates, and a molecule with N atoms will yield a representation of
 9

dimension 3N; use of internal coordinates (distances between atoms,

angles between bonds, etc.) may yield representations of dimension
3N - 6 (3N - 5 for linear molecules). All these representations can be
factorized into the irreducible representations whose characters are
given in Table 3, together with some additional information that will be
necessary for the applications to molecular spectroscopy.
To explain Table 3, we will use a typical example. Let us reproduce
part of the character table for the point group Z>3^, to which the planar
molecule BF3 belongs.

D
3 h
E 2C
3
3 2o , n
2S,3 3o,u

4 1 1 1 1 1 1
1 1 1 -1 -1 -1
1 1 -1 1 1 -1
1 1 -1 -1 -1 1
2 -1 0 2 -1 0 BF3 molecule
E" O£ -1 0 -2 1 0

In addition to the Schoenflies symbol of the group, the first line

contains all the symmetry operations that constitute it. The number 2
in 2C3 indicates that the group includes, in fact, the two C3 operations
C3 and c\ (rotations of 120° and 240° around the C 3 axis); but because
both operations have the same characters in all the representations, it
is unnecessary to repeat the column. The number 3 in 3C 2 indicates,
similarly, that there are three binary axes [through B F ^ , B F ^ , and
f 3)
BF in BF3], each one contributing an identical column to the table.
There is one reflection through a horizontal plane (the plane of the
molecule, which
1 is 2perpendicular to the principal axis C 3 ), to improper
rotations 5 3 and S 3 around the axis S 3 (coincident with £3), and three
reflections through the vertical planes (which contain C 3 and each one
of the C2 1 s). Addition of the trivial syiiimetry E completes the 12
elements of 0
Each one of the following lines of the table contains the characters
of one of the irreducible representations of the group, preceded by its
 10

Table 3. Character tables of point groups?

The D } groups

R; T

c E C,
t
A 2 1 a a
V xx* yy' azz* a
xy
B 2 -2 a . a
V V *y yz' zx

2vi
c
%
E c, cf c » e
3

A 2 2 1 R a + a . a
4 V z xx yy zz
r
e e | (a - a , a ), (a . a )
S xx yy' xy * yz* zx
I e eJ

c E C c"
* 4
A 2 1 1 i rp . R a + a 3, a
V z xx yy zz

1
B f1
-1 1 -2 a - a • ax
x® yy y
i
•
-2 fa .a, )
' W yz zx
E
t
-t -2 y

2vi
2 5
C E C c" C C
6 3
A 2 2 2 2 2 1 T ; R a + a.„, a
z z xx yy zz
B 2 -2 2 -2 2 -2
4 4
-e -2 -e
4
e
Ei 4 4 (T
x'Ty}' (R
x'Ry>
E
e -e -2 -e j

/
r 4 '4 «
-e -e 2 -e
E2 4 (a
xx - V V
C1 -e -e 2 -e " A
 11

The D } groups

E *

A I 1 R a
g
A J -1 T
u

A 2 2 2 2 +
V
B 2 -2 1 -2 o_
• V
Cl t
E
f12; -i
: ' 1 V
Jhri
C3 x I . 3
S S
A * l 6

2 2 a f a . a
9 t 4 arc yy' zz
e e e e
0 c
4

e
c eI "vy fa
xx " V V ; f
V
-2 -2
u 2 2i
e e -e -
4
4 (T.T )
c e •e x* y'

The C groups

E a j
A* 2 2 |9 T . TyS Z
a , a . a . a
xx* yy' zz' xy
A" 2 -2 S rz ; R.XT R„ a zx
11 8 y y*

| E C2 Ovlzx) ojtgz)

Ai ! 2 1 2 2 T
- z sx' i/y* zz
At 2 2 -2 -J R a
z xy
Bi 2 -2 2 -J T ; r a
X* y zx
2 -2 -2 2 T ; n a
1 y X yz
 12

C
E 2C
3v 3

Ai 2 1
N2 : T a -fa
z xx yy
At 2 2 -2 R
z
S 2 -2 0 T r a j
ra
< x> y * y xx • v v «

r
C K
4v
°2
At J 2 2 2 j T a -f a . a
3 xr yy' zz
A$ 2 2 2 -2 -l R
2
Bi 2 -2 2 2 -J a - a
xx yy
i>2 2 -2 2 -2 2
%
uP 2 0 0
-2
V 'V *zx>

2C
C
6v
E
6 2C
3 K K

Ai 2 1 S 2 2 2 T
8 a
xx * V *»
At 2 2 2 2 -2 -2 Rg

Bi 2 -J 2 -2 2 -2

Bt 2 -2 2 -2 -2 2

2 r
Ei

2
2 -2 -2 0 (T
X V V a
2 x;
Et -2 -2 2 0 0 fa
xx - V V
CM

E • • •

2 2 ... 2 T
2
a
xx
+ a .a
yy* as
S f 2 2 • . . -2
in

n 2 2 cos • . . . 0 (7 .r J; IT? ./? j fa

x y x y yz** <*„
ax.J
Et S A 2 2 COS 2$ .. . 0 fa - o, .J a )
xx yy xy
ft 5 2 2 cos 3$ .. . 0

• • • • • • • • « • • * • • •
 13

The GROUPS
: h

'2h
1 1 R (S * 0 . A . Q
2 xxJ yy' zz xj
B. -J -1 R , R a , a
X* Y yz zx
1 - -2 T
s
B -1 - 1 T t T
x' y
2TRJ
_ 3
'ih
1 R A + A > A
XX yy' zz

{
1 (<x a
xx - yy' v
J
>1" -J
-1 (a , a )
E" yz' zx
-I

E C CC
"4h C 2
%
1 1 1 1 1 J a + a , a
P xx yy zz
B -1 1 -1 -1 1 -1 a - a . a
9 xx yy' xy
i -1 •T T -1
fa. .a )
-i -J i -i -2 1) yz zx
J 1 1 -1 -2 -1
B -1 1 -1 1 -3

i -1 -i -i 1
-i -1 i i 1 i)
2ni
6
E C
6 C
3 I s\ % s
i E » O

1 1 1 1 J I 3 3 3 3 a
xx + V «„
1-1 1 - 1 1 J -J 3 3 -3

11 c -c* -1 -c C« 1 c -E« -C E«

I c* - C -1 c 1 C« -E -E 4

II - C * -C 3 -c J -E< -E -E4
fa
xx - V V
[3 - C -C« 3 -E 3 -C -C* -E
i]
1 1 1 1 2 7 -3 -3 -3 -3
-3
1-1 1 - 1 J -J -3 3 -3 -3

FL C -C< -3 -E E4 -3 -E E« E
"lu
1 C« -C -3 -C" C -1 -c* C -h
(1 -c* -c 1 -C1 -E e
i]
-3 E«
'2u
f3 -C -E4 I -C -E4 -3 E E4
 14

The D } groups

Pt M V E c2(?j c^iy) c-(x

A 3 3 1 2 a , a , a
XX* yy* zz
Bl 2 2 -3 -3 a
02 3-3 3 -3 a
V * * *x
Bi. 3-3 -3 3 a
1/*

P E 2C} 3C2
3
2 J 2
«SX +
V
A* 2 1 - 2 T ; R
B 0 ( V J ; (R^RJ
2 - 3
^xx " V V'' 'V

E 2C 4 C 1 - c" 2C 2
>4 4 2
3 3 3 3 3 a + a , a
xr yy' zz
A* 3 3 3 -3 -3
V
01 3 -3 3 3 -3 a - a
xx yy
0*
3 -3 3 -3 3 a
xy
ff 2 0 -2 0 (7 ( } (R
x>Ry> (
V y ' *yz'%x}

E 2C, 2C 3 Cf" 3C, 3C' -

2 2 2 2 3 3
°xx * V
3 2 1 2 -3 -3 V *2
01 2 - 2 3 - 3 3 -3
*2 3 - 3 3 - 3 -3 2
Si 2 3 - 3 - 2 0 0 (R
rr
x>y> x'Ry} (a
yz> a
zx>
2 -3. 2 0 0 (a
xx " V V
 ID

The D } groups

E C
f tc>2
- "d
Ai 1 3 ; 1 1 asr + 0yy'. a m
At 1 1 1 3 -1
81 1 -1 1 1 -1
B, 1 -1 1 -1 1 r
*
1
0 -z 0 0 11 V (R
X* V
*

E
I 2C

1
3C

1
2
L

l
2S

1
3ad

1 0XX V- 0yy a
zz
1 1 -1 1 1 -J R
z
2 -1 0 2 -J 0 a (a. a )
(R
*>V V xy'* yz, zx

1 1 1 -1 -2 -1
*Jm
1 1 -1 -I -1 1 T
z
1 2 -1 0 -2 1 0 T
II Sr Jy

E 2C4 1S c" 4C,

V
4d \
A1 J 1 1 1 1 1 1 0xx + 0yy*. a
ss_
Ai J 1 J 1 1 -1 -I
*s
Bi 1 -I 1 -2 1 1 -I
02 1 -1 1 -1 1 -1 1 7
z
2 S2 0 - A -2 0 0
<Tx>T»>
£2 2 0 -2 0 2 0 0 (a
xx
- ayy' . axy '
Ei 2 0 A -2 0 (tt
0 yz> "zx'

The D ^ groups

V V E C, z) CM C«(x) o[xy) o(zx) o'lyz)

2h * h
a
9 xx yy zz
F a
19 z xy
% R a
y sx
R a
39 X yz
»«
lu
2u
3u a
 16

E 2C 3 3C2 2S
»3h °h 3
A 1 2 2 2 2 2
i a + a J. a
1 1 -2 2 1 -2 R xx yy zz
*'2 z
E' 2 -2 0 2 -2 (T ,T ) (a. - a , a )
x y xx yy xy
A" 2 2 1 -2 -2 -2
1
A" 1 2 -1 -2 -2 2 T
z
E" 2 -1 0 -2 2 0
'vy 2/«. zx

E C 2C 2C' I 2S4
*C4 L
Z 2 2 a
h 2a
v
1 J 2 1 1 2 2 2 2 2 a +a ,a
s xr yy zz
1 2 2 2 2 2 -I -2 R
s z
1 -2 2 1 2 -2 2 2 .j a -a
®x yy
1 —2 2 •I 2 1 -2 2 -2 1 a
*y
-2 0 2 0 -2 0
** x* y ' V V
2 2 2 2 2 -2 -2 -2 -2 • 2
2 1 2 -2 -2 -2 -2 2 2 T
z
1 -1 2 1 -2 -2 2 -2 -2 2
1 -1 2 -1 1 -2 2 -2 2 -2
*2u
E 2 0 -2 0 0 -2 0 2 0 0 ?r ,T j
u x y

p E tC X «s fSs3
» f t °h
I t 1 1 1 1 I 2 aw • ayy', ii
a
J 1 1 -1 1 1 i
ff.' 2
2
2
2
cOS
cos
72* 3 cos 144° 0
144' 2 cos 72* 0
-1
2 2 cos 72° 2 cos 144° 0
2 2 cos J44° 2 cos 72° 0
rr .t ;
^a - a , a )
1 1 1 1 -1 -1 -J « W SV
Al" J
4," 1 1 1 -1 -1 -J -j 2 r,
£»" 2 2 cos 72° 8 cos 74:* o- -2 -2 cos 72• -2 cos 144° (p.ft) fa , a ;
El" 2 2 COS 244° S cos 72° 0 - 2 -2 cos 144" -2 cos 72°0 * V
 17

3C
E ** i <L "s
2 i 2 l 2 1 3 2 .2 3 a *•
V
2 J -2 -l 2 1 2 2 -2 -3 "m

'I.
1 -j 2 -l 2 -2 3 -2 2 -3
J -j -J 3 J 2 -3 -J 3
t.
>9
2 -2 0 0 2 1 -2 -2 0 0 (R.** RyJJ (a ,
% 23 2 0 -2
0 2 •2 2 0 (a
•V V
A
lu 1 2 -3 -3
1 -3 -2 -2 -2
'•2u 1 2 -2 -3 -3 -3 -2 2 3
B
lu 2 -2 3 -3 -3 3 -2 2 -3 2
*2u 1 -2 -3 3 -3 3 -2 2 2 -2
E
lu 2 -2 0 0 -2 -3 2 -2 0 0 (T. T )
£
2U 2 2 0 0 -2 3 2 ' -2 0 0

2C 2Sj

3 1 1 1 2 a m .a
see yy' a*
Z 1 •J 1 1 -2
9
0
2 cos •
0
2 -2 cos + 0
0
'vy
2 cos 2$ 2 2 coe 2$ a
9 • •• »•• ' « " V V
» • • • • • • • ft •ft«
3 1 -1 -2 -2
i 1 -1 -3 -2 2
n z 2 cos $ 0 -2 2 cos • 0
0 <**v
-u *
2 cos -2 cos 2$ 0
••• jj • • *
 18

T h e Cubic groups

2vi

1- 4C
3 < SC
2 e= e
3

A 1 1 1 1 oxx + ayy + azz

1 c e* 1
E ( aXX + ayy - 2a zz*, axx - ayy )
1 e* e 1

F 3 0 0 (T), (R) faxy , ayz . o zx)

- 11

E SC3 3C 6S 4
T
d 2
Ai 1 1 1 1 axx + ayy + a23
Az 1 1 1 -1
B 2 -1 0 (a + ayy - 2 aaz*. axx - ayy )
xx
3 0 — 7 1 (R)
3 0 -1 (T) r
V V

2-ni
2 3
E 4C
z
4C3 3C2 i
*ss 4S
l 3a.
h
E = e
A 1 1 1 1 1 1 1 1 axx + ayy + 22 a
9
1 e e* 1 1 e e* 1 (tx + a - 2a j
xx yy 22
F axx - ta/yJ
9 1 E* E 1 1 E* E 1
F 3 0 0 -1 3 0 0 -1
'v v v ("aXJ/. a2/Z, a2 J
J
9 X

Au 1 1 1 1 1 -1 ~1 -1
1 C z* 1 1 -E -E* —1
E
v. 1 e* E 1 1 -E* -E

3 0 -1 3 0 1 fT
F
u
0 0
*V V
 19

0 E tc2 3CJ ic4 6C2

Ax 1 1 1 1 1 c; -fa -f a
xx yy zz
A2 2 2 2 -I -2

B 2 -2 2 0 0 /a + a - 2 a , a - a )
XX yy zz xx "yy'
Pi 3 0 -2 1 -2 (RJ; (T)

Pi 3 0 -2 -2 2 fa , a , a J
xy' yz' zx'

E 8C, 3C"
2 SC i SS 3a ss 60
d
3 4 6 h o
1 J 1 1 1 1 1 I l = * a * 3S
a
A J J 1 -I -1 •»
J -L -i
29
E 2 -2 z 0 0 2 -1 2 0 faxr + a^ - 2 aas. n - a Ji1J
3
3 0 -1 -1
1 3 0 -1 i fa . a JS*, azxJ
v v
?
29
3 0 -2 -1 1 3 0 -1 _2 j
A
2U 1 1 1 J 1 -J -1 -1 -3
A J
2U
I 1 -1 -1 -J -1 -1 1 1
Eu 2 -1 2 0 0 -2 1 -2 0
-3 ft
F
lu 3 0 -1 I —s 1 -1 1 (T^ Ty. y
F
2u
3 0 -1 -1 1 -3 0 1 1
 20

conventional symbol. This symbol gives some information about the

characteristics of the representation, according to the following
convention:

• A one-dimensional representation will be recognized to be "symmetric"

or "asymmetric" with respect to a symmetry operation when the
corresponding character is +1 or -1 respectively. For two- and
three-dimensional representations the characters may be ±2 and ±3
respectively.
• A or B: one-dimensional representations which are symmetric or
antisymmetric, respectively, with respect to rotations about the
principal axis C .
• E: two-dimensional representations.
• F: three-dimensional representations (sometimes designated T).
• 1 or 2: subscripts attached to d's and S's to designate represen-
tations that are symmetric or antisymmetric, respectively, with
respect to rotations about a C 2 perpendicular to the principal axis.
If such a C2 does not exist, it is replaced by a cry.
• g or u: subscripts attached to all letters in groups with a center
of symmetry to indicate representations that are respectively
symmetric or antisymmetric with respect to the inversion through the
center.
• Primes or double primes: superscripts attached to all letters, when
appropriate, to designate a representation that, is symmetric or
antisymmetric,
+ respectively, with respect to reflection through a o,.
• 2 or 2 : one-dimensional representations for the groups of linear
molecules that are respectively symmetric or antisymmetric with
respect to reflection through a a y .
• n, A, 0, etc.: two-dimensional representations for the groups of
linear molecules.
The physical meaning of the symmetric or antisymmetric behavior of
the representations will become clearer after the explanation of their
use in vibrational spectroscopy.
 21

The right side of the character tables contains information about

the symmetry of the components of molecular translations (7), rotations
(i?), and polarizabilities (a). This information is given through their
assignment to the different representations and will be used in the
prediction of vibrational spectra. The symbol T i* an abbreviation for
the set Tx, T y , T,; the J? replaces Ry, tf, and means a ^ , * y y , a ^ ,
a , a.yz, a ^ . Degenerate components are enclosed in parentheses.

5. GROUP THEORY AND MOLECULAR VIBRATIONS

Up to this point we have mentioned only the symmetry of molecules

in their equilibrium configuration. But it can be proven that the
displacements of the atoms during molecular vibrations are constrained
to specific patterns determined by the molecular symmetry. This fact
results in a close relationship between the normal vibrations and the
irreducible representations of the point group. This relationship is
the basis for the application of the group theory to vibrational spec-
troscopy. The most important consequences of this application are: (1)
The normal modes of vibration can be classified according to the irre-
ducible representation to which they "belong." (2) This classification
provides some description of the normal modes because the character
table indicates if they are symmetric or antisymmetric with respect to
some symmetry operations; in this application, "symmetric" means that
the operation performed on the vibrating molecule will keep the vectors
representing the atomic displacements unchanged, while "antisymmetric"
means that the same vectors will change to the opposite direction.
(3) The degeneracy of the normal modes is given by the dimensions of
their representations. (4) The normal modes belonging to the same
representation as any component of a translation are infrared active.
(5) In the gas phase of symmetric top molecules, the vibrations in the
same representation as T are "parallel" and should show the typical PQR
structure. (6) The normal modes belonging to the same representation as
any component of the polarizability are Raman active; only the vibrations
belonging to the completely symmetric representation (all characters
equal to 1) can originate polarized bands.
 22

6. THE PREDICTION OF THE FUNDAMENTAL VIBRATIONAL BANDS

In this section we will describe step by step a procedure for the

calculation r-F the number and polarization of the fundamental bands that
should appear in the infrared and Raman spectra of a molecule of known
configuration.

Step 1: Assignment of the molecule to a point group

By working on a model or a good drawing of the molecule, one can

locate all the symmetry elements. There are no systematic procedures to
perform this step, but experience shows that a short practice period
will provide the necessary skills. It may be useful to look fiTSt for a
proper axis of rotation of the highest order. If none exists the molecule
can only belong to C , C., or C , and the search for a plane or center
S TS X
of symmetry will decide among them. If one or more Cp' s exist, select
the one of the highest order and determine in Table 2 the groups that
contain it. The left half of the list of symmetric elements can be used
as a guide to select which elements to look for next to reduce the
possible choices. This procedure should continue until only one group
is left and a careful check has been done to verify that no element
belonging to a higher symmetry group is present.

Step 2: Calculation of the characters of a reducible representation

Once all the symmetry elements have been located and the point
group has been determined, the characters of each symmetry operation in
a reducible representation of dimension 3N - 6 can be calculated according
to the following rules:

• For each operation E or C^: Count the number of atoms that are not
shifted when the symmetry operation is performed. Subtract 2.
Multiply by the appropriate factor in Table 4.
• For each operation i, S, or a: Count the number of atoms that are
not shifted when the symmetry operation is performed. Multiply by
the appropriate factor in Table 4.
 23

Table 4. Contribution to character per unshifted atom

Operation i H Operation i H
E 3 o 1
C2 -1 i -3
c\, cl 0 s
\> s3 -2
Cit, ck 1 S 4, Si* -1
c
5> c5 1.618 s
5> -0.302
C
S> C5 -0.618 f>5> S5 -2.618
C S
S> 2 6> S6 0

Step 3: Calculation of the number of fundamental vibrations belonging

to each representation (symmetry species)

In molecular spectroscopy, the irreducible representations of the

point groups are often referred to as "symmetry types" or "symmetry
species," and the reduction formula is slightly modified to account
explicitly for the fact that the columns of the character table may
contain more than one symmetry operation.
The number of fundamental vibrations of symmetry type y is given
by:

n
'-? Awi.
where
n- = number of operations in the ith column of the character
table,
a = number of columns in the character table (equal to number of
representations),
a
g = £ n. = total number of operations in the point group,
 24

X.£ = character of the reducible representation of the operations

of column i (determined in step 2),
xT = character of the y irreducible representation of the operations
of column i.
In some groups there are imaginary or complex characters, but they
always appear as conjugate pairs in two one-dimensional representations
which are the components of a degenerate mode E. When the reduction
formula is applied, the real sum of both complex characters has to be
used as the character for the species E. Notice that

,2^/n + g_2Tr£/n = 2 cos 2rr

i + (-£) = 0 and n

Step 4: Determination of the number of fundamental bands

in the infrared and Raman spectra

• Infrared spectra: will include all the fundamental modes with the
same symmetry as T , and/or Tg. The vibrations in the same
species as (T ,T)i7 or (T x ,T y ,T_)z will be double or triple degenerate
respectively.
• Raman spectra: will include all the fundamental modes with the
same symmetry as any component of a. The vibrations in the same
species as a ^ , a , a g g will be polarized (totally in the cubic
groups, partially in the rest). The vibrations in the same species
as axy a yz , and/or a zx will be depolarized.

EXAMPLES

7.1 AMMONIA (NH 3 )

Step 1

As a pyramid with the N at the cusp and - >J

the three H at the corners of an equilateral

triangular base, ammonia shows ICi (through /I
the N, perpendicular to the base) and 3o
 25

(through the C 3 and each NH bond). Inspection of Table 2 gives inmedi-

ately a point group C"3y.

Step 2

Atoms unshifted per symmetry operation:

=
uP = 4 , u_ = 1 (the N) , m 2 (the N, one H) ,
3 y

X£ . = (4 - 2)*3 » 6 , X C 3 = (1 - 2)*0 = 0 , x o • 2-1 - 2 .

Step 3
From the character table for the group £?3y:

n„ = 1 , n_ = 2 , n =3 ,
f
3 y

c = 3 , j » I • 2 • J s 6 i

s 2
N* = ^ [1*6*1 • 2*0*1 • 3*2*11 .

N^ = | [1-6-1 • 2*0*1 • 3*2*(-1)] « 0 ,

N 5 • £ [1*6*2 • 2*0*(-1) • 3*2*0) » 2 .

Ammonia has, therefore, two nondegenerate vibrations of species A\

and two doubly degenerate vibrations of species E. This result is
usually represented by

R = 2AI «• 2E .

Step 4

The character table shows that (1) all bands being infrared and
Raman active, each spectrum should show four bands; (2) in the Raman,
 26

the bands may be partially polarized and the E bands will be depolar-
ized; and (3) in the infrared spectra of gaseous ammonia the bands
are "parallel" and should show PQR structure.

7.2 MONODEUTERATED AMMONIA (NH 2 D)

Step 1 L
h
t\
There is only a a (through ND and bisecting
the two NH bonds). The point group is, therefore,
V
Step 2

U = 4 = 2
E ' "o

X £ = (4 - 2) • 3 = 6 , X{J = 2-1 = 2 .

Step 3

n„c = 1 = 1

o - 2 , g = 1 + 1 = 2,

N 4 ' = j [1-6-1 • 1-2-1] = 4 ,

N^" = j [1-6-1 + l-2-(-l)] = 2 .

Monodeuterated ammonia has, therefore, six nondegenerate vibrations

which can be represented by

T = 4/4' + 2/1" .
 27

Step 4

From the character table for the point group C s : (1) All bands
being infrared and Raman active, each spectrum should show six bands.
(2) In the Raman, the A' bands may be partially polarized and the
bands will be depolarized. (3) No prediction about the shapes of the
infrared bands of the gas can be made.
c
7.3 1.2-DICHL0R0ETHYLENE (cis) (c-C1HC-CC1H) k 1 CI
Step 1 ">H 7<-
r [y
r«
The plane of the molecule (o) and the
plane through the center of the C=C bond
and perpendicular to it (a') are planes
of symmetry. The intersection of both planes is a C 2 . There are no
other symmetry elements (except the identity) and the molecule belongs,
therefore, to the C 2 y point group.

Step 2

U = 6 0
E ' *C 2 " '

XE = (6 - 2)-3 = 12 , X ^ = (0 - 2) • (-1) = 2 ,

Mo = 6 , u = 0 ,
V

XQ =6-1=6, X =0-1=0
V V

Step 3

n
n
E = 1
' c2 • 1 • \ •1 • V = 1
'
<? = 4 , 0=1+1+1+1 = 4 ,
 28

M !
N = j [1-12-1 + 1-2-1 • 1-6-1 + 1-0-1] = 5 ,

Az j
N = j [1-12-1 + 1-2-1 • 1-6-(-1) + l-O-(-l)] = 2 ,

Bl !
N = j [1-12-1 + 1-2-C-l) + 1-6-1 + 1-0-(-l)J = 4 ,

BZ x
N = -J [1-12-1 • 1-2- (-1) + 1-6-C-l) + 1-0-1] = 1 .

Therefore

T = SA\ * 2A2 * 4Bi • B2

Step 4

From the character table of point group C"2y: (1) All bands are
Raman active and only the A2 bands are infrared inactive. There will
be, therefore, 5/1 \ + 4B! + IB2 = 10 infrared bands and 5A\ + 2A2 +
4Bi + IB2 = 12 Raman bands (of which 10 should coincide with the in-
frared). (2) The 5i4j Raman bands may be polarized; the rest will be
depolarized.

7.4 1,2-DICHLOROETHYLENE (trans) (t-ClHC-CClH)

Step 1

The plane of the molecule is the only

plane of symmetry and there is a C2 perpen-
dicular to it in the center of the C=C bond.
This center is also a center of symmetry.
Table 2 shows that the point group is C
 29

Step 2

U = 6 U 0
E » C2 = >

X E = (6 - 2)-3 = 12 , x C z = (0 - 2)*(-1) = 2 ,

u 0 = 6
i ' ' V '
'h

x { = 0*(-3) = 0 . xJ0 • 6'1 = 6 .

h

Step 3

n = 6 n = 1 n = 1 n - 1
E > C2 ' i ' ofc •

c? = 4 , g = l+ l +l+ l= 4 ,

A
N 0 = L [1*12*1 + 1*2*1 + 1*0*1 + 1-6-1] = S ,

N g = i [1*12*1 + 1*2*(-1) • 1*0*1 + 1*6*(-1)] = 1 ,

A .

N " = i [1*12*1 + 1*2*1 + 1*0*(-1) + 1*6*(-1)] = 2 ,

N B* = j. [1*12*1 + 1*2*(-1) + 1*0*(-1) • 1*6*1] = 4 .

Therefore

Y = SA + B
g g
+ 24u + 4 Bu .

Step 4

From the character table of the point group C (1) There will be
2Au + 4 B
u
= 6 infrared bands and 54g + ISg = 6 Raman bands; there should
not be any coinciding frequencies. (2) The 5*4 Raman bands may be
9
partially polarized; the B will be depolarized.
«7
 30

7.5 ETHYLENE (C2H,J

Cjto

Step 1
There are no C3*s or higher order axes,
but it i'j easy to find three perpendicular
(?2' s passing through the center of the C=C
bond — one coincident with the bond, one
laying in the molecular plane, and the
third perpendicular to the first two. Thus, the possible groups are
reduced to D2> or D The existence of the three planes of
symmetry determined by pairs of C2 decides in favor of D

Step 2
U = 6 U
C2 = 2
» = o , u^, = 0 ,
E '

\ ° 0
' u = 0 , u 2 , 6
o ' V = .

X E = (6 - 2) 3 = 12 , X r = (2 - 2)•(-1) = 0 ,
c2

x r . = C0'2).(-l) = 2 , = (0 - 2) • (-1) = 2 ,

X{ = 0-(-3) = 0 , X 0 = 0-1 = 0 ,

XQI =2-1=2, X0„ = 6 - 1 = 6 .

Step 3
n
E = 1
' n
C2 = 1
' r
'Ci = 1
' n^.. = 1 ,
2

n
i = 1
'
na = 1 ' , n0, = 1 , n
a" = 1
'

c? =8, g=l + l + l+ l+ l + l+ l+ l= 8 ,
A
N 9 = -g- [1-12-1 + 1-0-1 + 1-2-1 + 1-2-1 + 1-0-1

+ 1-0-1 + 1-2-1 + 1-6-1] = 3 ,

 31

N = -g- [1* 12* 1 • 1*0*1 • 1-2- C-l) • 1*2* (-1) + l'O'l

• 1-0*1 • 1-2-(-13 + 1*6*(-1)] = 0 ,

£
29
N = | [1*12-1 • 1-0-C-l) • 1*2*1 • 1-2-(-13 + 1*0*1

• 1-0-(-1) + 1*2*1 • 1*6*(-1)] = 1 ,

B
39
N = | [1*12*1 + 1*0*(-1) • 1*2*(-1) + 1*2*1 • 1*0*1

+ 1*0*(-1) • 1*2*(-1) • 1*6*1] = 2 ,

A
N " = ~ [1*12*1 • 1*0*1 • 1*2*1 + 1*2*1 + 1*0*(-1) • 1-0-C-l)

+ 1*2* (-1) + 1*6*(-1)] = 1 ,

B.
lu
U
N == i¥ [1-12-1 + 1-0-1 + 1-2- C-l) + 1-2-C-D • 1*0- C-l)

+ 1*0-c-l) + 1*2*1 + 1*6*1] = 2 ,

2u 1
N = 4-
8
[1-12-1 + 1*0*(-1) + 1*2-1 + 1-2-C-l) + 1-0-C-l)

+ 1*0*1 + 1*2*(-1) + 1*6*1] = 2 ,

3U
N = i [1-12*1 + 1*0*(-1) + 1*2*(-1) + 1*2*1 + 1*0-(-1)
+ 1-0*1 + 1*2*1 + 1*6* C-l)] = 1 •

Therefore

r = IA + B + 25, + A + 2B. + 2B + B .
g zg 3g u iw zu 3u

Step 4

From the character table of the point group D (1) There will be
2fl +
,„
1u
2B„2 u + IB-3 u = 5 infrared bands and 3.4 g + 1 B 02g
„ + 2B,3 g = 6 Raman
 32

bands; there should not be any coinciding frequencies. (2^ The

bands may be polarized; the other three Raman bands will be depolarized.

7.6 PHOSPHORUS PENTAFLUORIDE (PF5)

\
Step 1

There is an obvious C3 through the axial

fluorine atoms and each horizontal PF bond
coincides with a C T h e plane of the equa- tVN o^
torial fluorine atoms is a plane of symmetry.
These elements can be found in the D ^ group,
which can be verified by finding the 53 (coincident with C3) and the
3o (through C3 and each C 2 ).

2
step

U = 6 U = 3 W = 2
E ' C3 ' C2 '

% "4 '
4
"„ = » «<? = 1 »

X E = (6 - 2)-3 = 12 , Xc = (3 - 2)-0 = 0 ,

X ^ = (2 - 2) • (-1) = 0 , X_ =4-1=4,

Xs_ = 1-(-2) = -2 , X =4-1=4.

y

Step 3

nE = 1 , n„ = 2 , n„ = 3 ,
c
C3 2

m l n
S3 J = 2
' n
o " 3
»
\ - V

<2 = 6, g = 1 + 2 + 3+1 + 2 + 3= 12,

 33

'i
2 [1-12-1 + 2-0-1 «• 3-0-1 + 1-4-1 • 2* (-2) -1 3-4-1) = 2 ,

A\
= j2 [1*12-1 + 2-0-1 + 3-0-C-l) + 1-4-1 + 2-(-2)-1 + 3-4-(-1)] = 0

N 5 ' = J2 [1*12-2 + 2-0-(-« • 3-0-0 + 1-4-2 + 2-(-2)-(-l) • 3-4-0] = 3 ,

!
N =~ [1-12-1 + 2-0-(-1) + 3-0-1 + 1-4-(-1) + 2- (-2)-(-1)

+ 3-4-C-l)] = 0 ,

A"
2 [1-12-1 + 2-0-1 + 3-0-C-l) + 1-4-C-l)

+ 2-C-2)* C-l) + 3-4-1] = 2 ,

N^' = — [1-12-2 + 2-0-(-1) + 3-0-0 + 1-4-(-2) + 2* C-2)-1 + 3-4-0] = 1 .

Therefore

r = 2A\ + 3E' + 2A"z + E"

Step 4

From the character table of the point group CI) There will be
3E' + 2A'z = 5 infrared bands and 2A[ + 3E* + IB" = 6 Raman bands, the
frequencies of the 3ff* bands coinciding in both spectra. (2) The 2A^
infrared bands of gaseous PF5 should show PQR structure. C3) The 2A[
Raman bands may be polarized; the other four Raman bands should be
depolarized.
 34

7.7 CARBON TETRACHLORIDE (CC14)

Step 1
Ci

Each CC1 bond coincides with a

C3 axis and there are no C V s. This
/X
/ X
description is only compatible with ^cr
the groups T, T^, and T^. The fact \ ci
that every pair of C3's determines
a plane of symmetry decides in favor
/ /
V
of Tj. The existence of 3C2'S»
bisecting pairs of C V s , can be verified.

Step

U = 5 W = 2 Ur = 1 , Kc = 1 , U = 3 ,
E ' C3 ' C2 oJ

Xfi. = (5 - 2) • 3 » 9 , X C 3 = (2 - 2)-0 = 0

XC = (1 - 2)• (-1) = 1 ,

Step 3

n_ = 1 , = 8 , nc = 6 , n„ = 6 ,
" * ' "Cs " u ' n
C2 = 3
'

«? = 5 , gr = 1 + 8 + 3 + 6 + 6 =24,

j
N = Yx U'9'l • 8*0* 1 • $-1-1 • 6- (-1) • 1 • 6-3-1} = 1

^2
(1-9-1 • 8-0-1 + 3-1-1 • 6*(-1) -(-1) + 6-3-(-1)] = 0 ,
24
 35

U E = -ij [1*9*2 + 8*0* (-1) + 3* 1* 2 + G't-^'O + 6 ' 1 ,

F
1 1

N = i j [1-9-3 + 8*0*0 + 3*1* (-1) + 6* (-1) • 1 + 6*3*(-l)] -- 0 ,

+ +
N = yj [1*9*3 + 8*0*0 + 3-1- C-l) 6*C-1)'C-D 6*3*1] = 2 .
Therefore

r = AL + E + 2F2 .

Step 4

From the character table of the point group T^: CI) All four bands
should appear in the Raman spectra while only the 2F2 frequencies should
show in the infrared. C2) The Ai Raman band should be completely
polarized, while the other three bands should be depolarized.
 36

w 7\
- N . —

H
F i g . 2. Mono-

K deuterated ammonia.

Fig. 3. cis-1,2-Dichloroethylene.

Fig. 1. Ammonia.
 37

BIBLIOGRAPHY

A. Two books with the main emphasis on group theory:

F. A. Cotton, Chemical Applications of Group Theory, Interscience
Publishers (Division of John Wiley and Sons), 1963.
An elementary treatment of the basic thrjry and a clear description
of its application to molecular vibrations, molecular orbitals and
Ligand Field Theory.
J. R. Ferraro and J. S. Ziomek, Introductory Group Theory (and its
Application to Molecular Plenum Press, 1969.
Structure),
A practical guide for "scientists with only limited theoretical
background." Includes detailed examples of calculations for
several point groups.

B. Two classical references:

G. Herzberg, Molecular Spectra and Molecular Structure. Vol. II:
Infrared and Raman Spectra of Polyatomic Molecules, D. Van Nostrand
Company, 1945.
A comprehensive treatise with extensive data on most molecules
studied until its publication. Group theory is not used explicitly,
but tables are given for the determination of the symmetry and
activity of fundamental, overtone, and combination bands.
E. B. Wilson, J. C. Decius, and P. C. Cross, Molecular Vibrations,
McGraw-Hill Book Company, 195S.
The undisputed principal reference for the theoretical treatment
of molecular vibrations. Few practical examples, but. a complete
chapter is devoted to the detailed analysis of benzene.

C. Books on general molecular spectroscopy with at least one chapter

on symmetry and group theory:
G. M. Barrow, Introduction to Molecular Spectroscopyt McGraw-Hill
Book Company, 1962.
N. B. Colthup, L. H. Daly, and S. E. Wiberley, Introduction to
Infrai'ed and Raman Spectroscopy, Academic Press, 1964.
 38

G. W. King, Spectroscopy and Molecular Structure, Holt, Rinehart

and Winston Company, 1964.

K. Nakamoto, Infrared Spectra of Inorganic and Coordination Compounds,

John Wiley and Sons, 1963.

D. Steele, Theory of Vibrational Spectroscopy, W. B. Saunders Company,

1971.

D. Two advanced books on group theory:

E. Wigner, Group Theory, Academic Press, 1959.

V. Heine, Group Theory and Quantum Mechanics, Pergamon Press, 1960.