UNIT 2 SYMMETRY OF MOLECULES

/
Structure
2.1 Introduction
Objectives
Valence Shell Electron Pair Repulsion (VSEPR) Theory
*
Symmetry Elements and Symmetry Operations
Rotation about an Axis of Symmetry
Reflection in a Plane of Syminetry
Improper Rotation about an Axis of Improper Rotation
Inversion through Centre of Symmetry
Identity
Point Groups of Molecules
Some Implications of Molecular Symmetry
Dipole Moment and Molecular Symmetry
Symmetry and Optical Activity
Spectra and Molecular Symmetry
2.11 Summary
2.12 Terminal Questions
2.13 Answers
2.14 Appendix

/ The molecules with different structures show different ,reactivity pattern and
molecular spectra. The question arises, "is there any way to relate structure, spectra
and reactivity?". Such a relationship could help us both in understandig the nature of
known substances and in predicting the properties of new ones. In this unit, we are
going to discuss symmetry aspects of molecules a n 4 we will indicate h0.w symmetry
could relate structure (or shape) to spectra (or to many of the physical properties).

I In Unit 3 of CHE-01 (Atoms and Molecules) course, we have discussed

the way of writing the Lewis structures of molecules (and ions) and

1 predicting their shapes on the basis of valence shell electron pair repulsion theory.

As a continuation of the same, we shall relate shape of a molecule and symmetry

aspects in this unit. We shall show how to classify molecules as point groups based on
symmetry. We shall state the uses of point group classification in understanding the
physical properties such as dipole moment, optical rotation and spectra. Some of the
aspects of symmetry are covered under group theory in the Appendix part of this unit.
We shall also indicate the uses of group theory in understanding the chemistry of
molecules. In this unit, we shall attempt a qualitative treatment of molecular symmetry
and group theory.

Objectives
After studying this unit, you should be able to:
define symmetry elements and symmetry operations,
state the list of symmetry elements in simple molecules,
identify the point group of a molecule from the list of its syinmetry elements, and
state the implications of molecular symmetry.
t
Bmk CoDopb and Ibbtid
Smn 2.2 VALENCE SHELL ELECTRON PAIRREPULSION
(VSEPR).THEORY
It is worth recapitulating valenceshell electron pair repulsion theory which has been
dlacussed In Unlt 3 of CHEOl course. The VSEPR theory helps us to explain the
shapes and bond angles of molecules ia relation to the number of shared and lone
electron pairs around the central atoms.

We present ia Table 2.1 the shapes of different molecules and ions according to
VSEPR theory.

Table 2.1: Number of Electron Palm In the Valence Shell of the Central
.
Atom, and shape of Molecule or ion.

No. of Electron Palm

Total Bond Lone Shape Examples
pairs palm
2 2 0 linear H g q , BeCb
3 3 0 triangular planar BF3, BC13, c@-, NO;

4 4 0 tetrahedral c&,B q ,mt

4 3 1 trig04 pyramidal m 3 , PF3
4 2 2 angular HzO, IC$, NH;

5 2 3 linear XeF2, ICG

6 6 0 octahedral SF6,PF;
6 5 1 square pyramidal IF^, she-
6 4 2 square planar .BrFT, XeF4

SAQ 1
Using VSEPR theory, predict the shape of PC&. Draw its structure.

23 SYMMETRY ELEMENTS AND SYMMETRY

OPERATIONS
I
In the last section, we saw bow molecules can be classified on the basis of shape. It is
better to classify the molecules based on their symmetry aspects. This could help us to i
understand the molecular properties such as dipole moment, opticalI
activity and I
i

i
 I'

spectral characteristics. Bcforc trying to classify molecules on the basis of symmetry, Symmetry of Molecules
we must understand the terms, symmetry elements and symmetry operations.

Symmetry operation is tbe movement of an object such that it leaves the object
looking the same. A symmetry operation brings the molecule into the equivalent or
identical configuration. You cab understand the words 'equivalent' and 'identical'
configurations by using a cardboard which is shaped like an equilateral triangle (Fig.
2.la). You label the three vertices of the triangle as 1,2 and 3. Rotation of the
triangular cardboard through l'2V (2n/3) and 2400 (4n/3) in the anticlockwise
direction gives rise to equivalent configurations i.e., each configuration is
indiitinguishable from the original configuration (Fig. 2.1 b and c) whereas the
rotation through 360"( 2 4 results in an identical configuration (Fig. 2.1 d). In
equivalent configuration, the positions of the atoms in space are similar to those in the
original configuration, i.e., before applying symmetry operation. In identical
configuration, the positions of the atoms are the same as before applying symmetry
operation. (Compare Figs. 2.la and d).

(r

PI, 2.1: (a) The conflgumlton before rotallon; (he dotted line shows the axls ofrotatlon In a
dlrecuon perpcndlcular to the plane of the moltculc
@) and (c) equivalent c o n ~ u r a t l o n(after
s .ntlclock.r(se rolatlon through 1UP (2 n / 3 ) and
2w (4 ~ 1 3 ) .
(d) IdenUcaI conflpnaUon (after rotatlon through 3600 (2 n)).

Similarly, reflection once across a plane passing through equilateral triangle type
molecule can give rise to equivalent configuration, while another reflection through
the same plane gives rise to identical configuration. For instance, imagine a Rotation through IW once,
perpendicular plane passing through vertex 1of the equilateral triangle-shaped
cardboard. This perpendicular plane is shown as a dotted line in Figs.2.2 a and b.
Reflection through this plane once results in equivalent configuration, Fig. 2.2b.
<
rwice and thrice can be
denoted by c:, and
also represents threefold
C3

Another reflection through this plane results in an identical configuration, Fig. 2.2~. axis of rotation. We shall
discuss this in a detailed way
in thc next section.

(a) (b) (4

Flg. 22: a) The conflgunatlon before mflectlon.

, b) The equlvaleni ~nfIgura1lunrcsultlng from reflectlon through a ptrpendlcuhr plane
(shown as dotled Une passlng through the vertex 1).
c) The Identical conflpmtlon resulting from another reflectlon through thc same plan*
 C o n a ~ t 8 a n dRotational So far we have seen rotation about an axis and reflection across a plane which are two

I smm
The .,mmetyeIement i ~ line
. p h n e or a point whereas the
SyXnQlety operation is the
of the five symmetry operations. All the symmetry operations are listed in Table 2.2.
a or Corresponding to each symmetry operation, there is a symmetry element. The
symmetry element is a line or a plane or a point with respect to which the symmetry
operation pcrfonned to bring the operation is performed. The symmetry element is a geometrical property which is said

configuration.
.
object into an eauivulent
~~- ~
to generate the operation. Table 2.2 lists the various symmetry elements and symmetry
operations.

Table 22: Ldst of Symmetry Elements and Symmetry Operations

S. No. Symmetry Element Symmetry Operation

Wc will be using the same 1. n-fold axis of symmetry or proper Rotation once or several times by an
rymbois for each pair of oyrmetry axis of symmetry (C,) angle (equal to 360°1n or 2 n/n) about
clements and symmetry the axis; n must be an integer.
operations. These symbols are
indicated within brackets under 2. plane of symmetry (a) Reflection plane passing through the
thc column 'Symmetry element' in
Table 2.2. molecule
3. Axis of improper rotation or Rotation about an axis by an angle
alternating axis of symmetiy or 360"tn or k / n followed by reflection in
rotary-reflection axis (S,) a plane perpendicular to the axis of
rotation
4. Centre of symmetry (i) Inversion of all atoms through the
centre of symmetry
5. Identity element ( E ) ~ o i nothing
n ~ to the object

The crystal symmetry includes

translathat s y m m e t ~ w h e x u ; At least one point in the molecule should be unaffected by all the symmetry
symmet~docs not
include it. operations. Also, all the symmetry operations possible for a molecule must intersect at
this point. Thus, the symmetry operation should not lead to translational motion of the
molecule in the space. TKs is the basic differencebetween the molecular symmetry
and crystal symmetry.

This aspect will be made more clear in Sec. 2.9 where we shall distinguish between
molecular point groups and crystallographic space groups. We shall explain the
symmetry operations and symmetry elements in a detailed way in the sections to follow.

SAQ 2
Draw a square and label the corners 1,2,3and 4. Also through diagrams indicate the
equivalent configurations and the identical configuration arising out of rotation
through 90" successively four times through an axis perpendicular to the square b

surface.

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..........................................................................................................................................................
..........................................................................................................................................................
-
2.4 ROTATION ABOUT AN AXIS OF SYMMETRY
The n- fold axis of symmetry (or the proper axis of symmetry) is a line about which a
molecule is to be rotated through 360"/n( or &/n or a)to obtain an equivalent
configuration. The symbol for n-fold axis of symmetry is C,. The subscript 'n' in C, is
called order of an axis which can be defined through Eq. 2.1.
 360" Symmetry of Molecules
Order of axis = n =
Minimum angle of rotation (a)for obtaining ...(2.1)
Note that
In the case of water molecule, rotation through 180" (= 360"/2) results in an
equivalent configuration.

Hence,

i.e., H 2 0 molecule has a twofold axis of rotation (C2 axis). C2 axis of H 2 0 is illustrated
in Fig. 2.3 along with the rotation through C2 axis once (c:) and twice (a; C: stands
for 180"rotation once and stands for 180" rotation twice. The twofold axis of water
is on the same plane as the oxygen and hydrogen atoms.

The subscripts 1 or 2 are used to

indicate the interchanging of the
hydrogen atoms.

Flg. 2.3: Twofold Pxls C2 In wakr mokcuk; the e&ct of one C2rolation (cS Is shown by
Interchpap of HI and H2 a h m a AppllcaUoa of C2M c e (6 briogs the molecule to
Idtntlcd conflprntion as lndlcakd by the posltion of HI on tht Iefl side and Hz on the
rlght side

In general a n-fold axis of symmetry (Cn) gives rise to c;, c,.......c," operations, and,
For C2 rotation,

c,"=E ...(2.2)

where E refers to identity operation. Identity operation means doing nothing to the
molecule and after performing an identity operation, the molecule regains identical
configuration. A rotation through 360" (c,") is an instance of identity operation.

Note that c,"means n times rotation about Cn axis. We shall see shortly other ways of
carrying out identity operation.

Note that as per Eq.2.2 in 3 0 molecule, rotation through C2 axis twice leads to
identical configuration.
i.e., c~c~,=c$=E The rotation operation by
2 n/n (= a)is denoted as C (a).
The presence of C3 axis in NH3 can be understood on the basis of the fact that rotation
through 120" about this axis results in an equivalent configuration. Using Eq. 2.1,

The C3 axis of NH3 is shown in Fig. 2.4a.

Thb rotations through 120", 2409 and 360" are denoted by the symbols C& and C'y
4
respectively. The operations C: and lead to equivalent configurations while leads C:
to identical configuration. The equilateral triangle formed by joining the positions of
three H atoms can be used to represent the effect of successive rotations by 120" three
 Basic Concepts and Rotational
Spectra
times. For this, use Figs. 2.1 a-+Figs. 2.1 b, c and d are the results of c:, and
operations. You can understand these operations using the figures given in the margin.
C: <
The rotations, c:, and in <
NH3 and BF3can be explained In other words, a threefold axis of symmetry gives rise to three operations,
using the figures given below. As
fares NH3 molecule is concerned,
c:, and 4.
it must be rcalised that the three
vertices of the equilateral triangle Also C:C: = ...(2.3)
represent the three .iydrogen
a t o m of NH3 while niMgen atom i.e., rotation through 240. is equivalent to rotation through 120" twice.
is abwe the plane of equilateral
triangle so that the shape of the Further, Gc:=G=E ...(2.4)
molecule is trigonal py-ramidal. In
case of BF3, the three vertices of i.e., a rotation by 240" after a rotation through 120" is equal to rotation by 120"three
the equilateral triangle represent
times (CJ3 or rotation by 360.. The operation is ecjlivalent to identity operation,E.
the three flourine atoms and the
boron atom is also in the plane of
this triangle in keepingwith the The differencebetween the trigond NH3 and planar molecule
triangular planar shape of BF3 BF3 can be seen from the fact that these have different numbers of axes
1 molecule.
of symmetry. For example, N q has only oi symm6try but BF3 has one

Let us e x k i n e benzene molecule. Benzene has one C6 axis (perpendicular to thd

molecular plane) and six C2 axes (Figs. 2.6 a-b). Three of the C2 axes pass through

(a)

Flg.2.4: (a) The shape of NH3 moleculc--(dpnol (b) The top vim of NH3 molecule which Lr '
pyramidal; polnt 0 lles ln thexy plane used in drawlng the figures given at the
(shown P8 shaded area) and on (he z uds margin to denote C& <and 4
which Lr C3axh pasing througb operations.
nllrogen atom The thra hydrogen
sloms form an equilateral lrlpngle In the
*y plane.
 Symmetry o l M o l e c u l ~

Flg. 2.5: (a) The rhape of BP3 molecule - @) Threefold udr of 8ymmclry In B q ;I1 la perpendlculer lo the
t r l a n p l a r planar molec~~larplane. The molecolar plane b rhown by the shaded
-
area. Fhch B F bond b dm a hvofold axlr ofsymmetry. All the
t h m C2axes are In the molecuhr plant.

Flg. 2.6: (a) C6Inbennne; It Is perpendicular to the molecder plane (shown M shaded uea) Since n = M a ,n tends to infinity
as a tends to zero. A h note that
@) The three C2axes along opposlle C H bonds and three C2axes la behveen parallel .' a is continuous angle
C-Cbonda'

Linear molecules such as Hz, HCl, C02, COS, etc. ham C, axis along their molecular
axes since rotation through even any small angle gives'rise to an equivalent
configuration. In other words, the angle of rotation for obtaining equivalent
configuration is infinitesimally small (i.e., a -. 0) for linear molecules such that
application of Eq. 2.1 leads to the conclusion that n = a.

Using the above ideas, answer the following SAQs.

SAQ 3
You have predicted the shape of PC&in SAQ 1.Name the axis of symmetry in PC4 .

...........................................................................................................................................................
Basic Concepts a n d R o t a t i o n a l SAQ q
Spectm
State the symbols for the operations of six successive rotations through C6 axis.

2.5 REFLECTION IN A PLANE OF SYMMETRY

A plane bisects the object under consideration so that one half of the object on one
A vertical plane p s e s through sidc of the plane is thc mirror image of the half on.the other side. If the plane contains
principal axis. IIence a, and a ;i n the principal axis, it is called the vertical plane and is denoted by a,. H 2 0 has two
H ~ arc
O vertical planes. vertical planes of symmetry (a, and a: -Figs. 2.7. a and b) while NH3 has three vertical
A horizontal plane (ab)is
perpendicular t o the principal axis.
planes of symmetry a, ,a,,' and a:' (Fig. 2.8).

PIE 2.7: a) %a verllcal planes u l symmetry Flg. 211: The three vertlcul planes o f symmetry in
(a, a n d q')In waler. NII, (a,, a; und a;' ); each vertical plnne o f
1 symmetry encloses one N-H bond also.
b) q pLqm
1
16:differently s h w n w, that It
b ellfikr to visrullse the two planes

The terms 'conformation' and

'configuration' have to be properly Whcn thc planc of syrnmctry is perpendicular to the principal axis, it is called the
understood. Various conformations horizontal planc, and, is denoted by ah.For instance, the plane containing all the six
o f a moleculc result due t o rotatien
about C - C bond through different carbon atoms and six hydrogen atoms in benzene is the horizontal plane, since it is
angles. For insiancc, ethane has two perpendicular to the (Cb)principal axis.
well known conformations, cclipscd
and staggered. For a better
understanding o f the term, Again Ict us examine thc simple cases of NH3 and BFJ. The fact that their shapes are
conformation, rcfcr t o .kc. 3.7 o f different is shown up by the prescnce of different types of planes of symmetry. Thus,
U n i t 3 o f Block 1 o f Organic
Chcmistry (CIIE-05) coursc.
both thcse molcculcs have three vertical planes of symmetry. In addition to these, the
planar molcculc, BF3, has a horizontal plane of symmetry but not NH3 (which is
The termiconfiguration' refers to a
particular spatial arranpment o f pyramidal).
atoms i n a molcculc. 'lhc optical
isomers and geometrical isomcrs
come under this category. I n this
Wc shall also cxaminc anothcr typc of plane of symmetry which is known as dihedral
context, you may rcfcr to Sec. 2.2 o f planc and is dcnotcd by ad.A dihedral plane must be,
U n i t 2 o f Block 1o f Organic
Chcmistry course. i) vertical (i.e., must contain the principal axis) and
ii) bisect the angle bctween two C2axes which are themselves perpendicular to the
principal axis.
For instance, the staggered form of ethane (Fig. 2.9a) has three dihedral planes. Each
dihedral plane contains the C3 axis (which is the principal axis) and intersects two
mutually perpendicular C2axis. One of the three dihedral planes is shown in Fig. 2.9b.
c-

- -
Pis 2.9: (a) The slaggercd conformelion of ethane I1 hns lhme adplanes and each adplane
conhlns C C bond end a pair of C H bonds.
One of (he dihedral planes shown by the shaded portion.
b)

The operation of reflection of same type (viz. vertical, horizontal or dihedral)

conducted twice across a plane leads to identity operation:
i.e., a,a,= E
Oh Oh = E

adad = E 1
Having studied the above, answer the following SAQs.

SAQ 5
Name the planes of symmetry in PC&. For its structure, refer to SAQ 1.

SAQ 6
SOCG is pyramidal in shape. It has a plane of symmetry. Identify the atoms on this
plane.

Hint: There is a simple restriction on the planes of symmetry. A plane must either pass
through an atom or else that type of atom must occur in pairs being placed
symmetrically on either side of the plane.
Basic Concepts and Rotational
Spectra 2.6 IMPROPER ROTATION ABOUT AN AXIS OF
IMPROPER ROTATION
In the Appendix part, wc shall
An n-fold improper rotation codsists of n-fold rotation followed by a horizontal
discur the importance of
combining operatione such as in
reflection. Improper rotation about an axis is also known as rotary-reflection
Eq. 2.6 operation. Such an axis is called rotary-reflection axis or alternating axis of symmetry
or improper axis of symmetry (S,,).
In P(pudichlomethylene, S2
being quhnlent to C2 operation To cite an example, the staggered conformation of ethane has improper axis of order
followed by q,can be rhown as 6(S&.To illustrate thii fact, the rotation of the staggered conformation of ethane by
follows: 60" (Cd followed by reflection through the horizontal plane (ah)has been shown in
Fig. 2.10. You can see from this figure that C6 followed by ahwhich is equivalent to S6
leads to an equivalent confiation.

To understand the displacement

of psrticular hydrogen or chlorine
atoms, the rubecriptr 1 and 2 are
uoed. Also note that Sz is
t equivalent to i, the inversion F l s 2.10: S6 In stag~eredconformation of ethane shown In krmr ofC6 and a,,,
operation,which wc shall dimcuss
in the nut section. The presence of improper axis of symmetry in a molecule may seem difficult to
identify. But it is useful for deciding whether a molecule is optically active or not. This
aspdct will be made clear in Subsec. 2.10.2 of this unit. Your understanding of this
section can be verified by answering the following SAQ.

SAQ 7
The staggered conformation of ethane has S6axis. What do you mean by this?

2.7 INVERSION THROUGH CENTRE OF SYMMETRY

Inversion is the process of drawing a line from any point through the centre of the
molecule to an equal distance on the other side from the centre to drive at an
equivalent point. The centre of the molecule which generates inversion is called the
centre of symmetry or the inversion centre (i).
All homonuclear diatomic molecules (e.g., Hz, N2, etc.) possess the centre of Syn~n~etry
oFMoleculcv

symmetry. Also C02, C2H4(Fig. 2.11), c6H6, SF^ and the staggered conformation of
ethane possess centre of symmetry.
H\ /H
H20, NH3, BF3 and CH4 do not possess centre of symmetry. In Sec. 6.6.3 of Unit 6 of
Atoms and Molecules course, we have indicated that the presence of centre of H
symmetry in a molecule leads to zero dipole moment for the molecule. We will recall
this idea in Sec. 2.10.1 of this Unit. Similar to reflection, the operation of inversion ~ 1 2.11:
~ .~h~ dot represen& tile
conducted twice through the centre of symmetry leads to identity operation. centre ur syrnrnet~in
ethylene.
i.i = E ...(2.7)
Answer the following SAQ. ,

Note that i is a special case of

improper rotation. when the
SAQ 8 angle of rotation is 18V
(a = 2x/2 = x).
What do you think could be@e dipole moment of benzene? Also a, C?= S? = i
State the reason. This relationship has been
illustrated using
..........................................................................................................................................................
rratrr-dichioroethylcnc in the
previous section.

2.8 IDENTITY i

The operation of identity (E) consists of doing nothing. The corresponding element is
the entire object. All molecules possess identity element. One reason for its inclusion
is that some molecules (e,g., CHFClBr, Fig. 2.12) have only this symmetry element;
another reason is connected with one of the fundamental aspects of group theory
(which we shall mention in the Appendix of this unit). We have already mentioned the
relationships of rotation, reflection and inversion with identity operation through Eqs.
2.2,2.5 and 2.7. \
Fig. 2lJ:Qulnolinc

FIB 2.12: CAFClBr which has on1y idenllly M (be element 01 symmetry.

So far, we discussed in detail the symmetry elements and symmetry operations. In the
next section, let us see how the molecules can be classified according to symmetry. HOOC

2.9 POINT GROUPS OF MOLECULES F I ~214:

. teso-(orter~c.EM
I
Point groups of molecules are classes of molecules which have same list of symmktry
elements. Thus, CH4 and CC14, have same list of symmetry elements and, belong to the
The method of identifying point
same point group, and, are different from the point group to which H20belongs. The groups of molceulcs has been
classification of molecules into point groups is of help in understanding the spectral discussed in the Appendix.
characteristics, dipole moment values etc. of molecules.
47
Basic Concepts and Rotational A molecular group is called a point group because onc point in the molecule remains
Spectra rued under all the symmetry operations in the molecule. All the symmetry elements of,
a molecule intersect at this point. We may note that crystals have an additional
element of symmetry known as translational symmetry, wherein symmetry arises from
the translational motion of crystals through space. The crystals are classilied into
space groups. We are not going to discuss crystallographic symmetry in this unit.

The point group of a molecule can be denoted by a specific symbol. There are two
kinds of notations, one devised by ~ c h o e n f l z and,
s the other, by Hermann and
Mauguin. The Schoenflies notation is more common for the discussion of molecular
symmetry and the Hermann- Mauguin symbolism is exclusively used for the
discussion of crystal symmetry. In Table 2.3, we shall give the Schoenflies notation for
Flg. 215: 1120(parllally
2 opened some of the point groups.
book conIlgurn(lon)

Note that all dihedral groups have Table 23: Schoenflies Notation for Some Point Groups.
a C, axis and nC2 axes
perpendicular to C, axis. The
Schoenflies Symmetry Examples
dihedral groups mentioned in notation elements
Table 2.3 are
D3, D3j,. D6b,DM and Dmh.

cs aand E Ouinoline (Fig. 2.13)

ci (sd iandE meso-t artaric acid (Fig. 2.14)

c2 C2 and E Hz02(partially opened book

configuration (Fig. 2.15)).

FIB 2.16: [Co (en),]'+ ion ;en Ch, C2, 2 a,, and E H20 and SO,
stands for ethylene
dlamlae
C3v 2 C3, 3 a, and E NH3 and CHC13

c-v 2 C,, -av and E Linear molecules without centre of

symmetry such as CO, OCS and HBr

c2h C2, ah,i and E trans-l,2-dichloroethylene

D3 C3, 3C2 and E [Co en)^^' (Fig. 2.16)

D3h 2c3,3c2,ah, 3 2s 3 BF3, PC5 (Fig.2.17) and eclipsed form

and E of ethane

Fig. 217: PC&: notr lhal the

verllcal CI-P-CI bonds Dm, 2c,, -c2, O0% ah, All linear molecules with centre of
ronstltute C, axla symmetry such as Hz, C12 and %HZ
2S,, i and E
A group is called a cubic group, if
it has many C, axes of order 2C3, 3C2,3ud,i,X6and E Staggered form of ethane
D~
greater than 2. The important
cubic groups are Td and Ok
Td 8C3,3C2,6S4,6 adand E CCL and CH4 (Fig. 2.18)

Oh 6c4,8c3,
6c2, Oh, a 4 SF6 (Fig. 2.19)
8S6,6ud,ia n d E
 Symmetry d Molecmlee

Fig. 218: a) Methane belonging to Td group; the three carteslan axes serve as three C2 (and a h SS
axes. The four C3axes are dong (be four C -H bonds (these C3 axes are also (be body
dlago~ls-MT, NS, OR and QP); one of the C3pxes (QP) Is showa
b) You can make slr triangular planes In a tetrahedron by comblnlng any two corners
wlth the centre; do not confuse these six planes wlth four faces of the tetrahedron whlch
are obtained by Joining any three corners only. These slx planes M Qd for CH4;each
of the adpasses through the carbon and two hydrogen atoms and relates the other two
hydrogen atoms as a mirror h P g e of each other.
c) One of the slr dihedral planes (ad).

Fig. 219: SF6wlth'Ohpoint group symmetry; SF6Is shown lnslde the cube
(a) k h F - S F linear arrangement Is a C4ards; the three C4axes are a t rlghl angles to
each other
@) Four C3axes M located along the body.dlagonals (MT, NS, OR and QP) of the cube;
one of the C3a s (QP) Is showa

(c) One of the three ahplanes b shown by the shaded are- ench ahplane comprbes of two
d l a p m i units of F-&F; other symmetry elements are not showa

Using the above materials, answer the following SAQ.

SAQ 9
Using your answers for SAQs 1,3 and 5, identify the point group of PC&.
Basic Concepts and Rotational
Spectra

2.10 SOME IMPLICATIONS OF MOLECULAR ,

SYMMETRY
The examination of molecules with respect to symmetry aspects could lead us to many
useful conclusions. We shall examine a few of them.

You are advised to study Secs. 6.4

to 6.6 and the Appendix portion 2.10.1 Dipole Moment and Molecular Symmetry
of Unit 6 of CHEO1 (Atoms and
Molecules) course to understand Dipole. moment is a vector quantity as defined in Sec. 6.4 of Unit 6 of CHE-01 (Atoms
the dipole moment concept. and Molecules) course. It has both direction and magnitude. The symmetry operation
allowed for a molecule should not affect the direction or magnitude of the dipole
The statement that the dipole moment vector. In other words, the dipole moment vector should be invariant and
moment v t d o r should be must be contained in each of the symmetry elements of the molecule. As a result of
invariant (or totally symmetric)
with respect to symmetry
this, only molecules belonging to the groups Cn ,Cnvand C, may have dipole moment.
operations will be used in defining
the allowed transitions in the Let us illustrate this using Hz0 molecule. As explained in the Appendix of Unit 6 of
Appendix of this unit.
CHE-01 course, the direction of the resultant dipole moment vector in H20 (indicated
by $ sign) is as shown in Fig. 2.20a.
You try C2,uvor u.,'operation
(using Fig. 2.20b) through
diagrams such as Fig. 2.3 and
verify the fact that the dipole
moment vtctor remains invariant
after each symmetry operation.

Flg. 220: lllmtration of the fact that each of the symmetry elemenls of water conWns the dlpole
moment vector. It Is worth recollecting that H20has E, C2and 2 uvM symmetry
elements.
a) H t O stands for 0-H bond moment and $ stands for the dlrcctlon of the resultant
dlpole moment vector. Note that the dlpole moment vector Ues along the C2hxb.
b) Both uvand u.,' planes conWn the dlpole moment vector. @) h drawn to show that uv,
Note that molecular symmetry is a u.,' and C2contnin the dlpole moment vector.
theoreticat concept. Experimental
quantities such as dipole moment
o r absorption frequencies As shown in Fig. 2.20 a-b, the symmetry elements, C2 axis and two uv planes, also
(obtained from spectral contain the resultant dipole moment vector in H20 molecule.
measurements) help us in
confirming the theomtical aspects
such as symmetry of a molecule. In molecules with the point groups such as Cnh,D,, Dnh,etc., there are symmetry
operations that correspond to turning the molecule upside down. This would reverse
the direction of the dipole moment vector which is not allowed. Hence, the molecules
belonging to the point groups such as Cnh,Dnhetc. cannot have dipole moment. Use
The presence or absence of dipole moment tells us about thesymmetry of the molecule. Symmetry of Molecules
We shall illustrate this taking two cases of triatomic molecules, H 2 0 and C02. H 2 0 has a
dipole moment value of 6.14 X 10-jDC m. This wnfirms the bent structure of H 2 0 (as It is worth recapitulating that the
bent structure df H@ and the
predicted by VSEPR theory in Sec 2.2) and the fact that it could belong to the point group
Chr (a special case of C, which has permanent dipole moment). linear structure o f C 0 2have been
explained in subscc. 6.6.3 of Unit
C02 has zero dipole momebt. This confirms the linear structvre of Co2 (as predicted 6 of CHE-01 (Atoms and
Molecules) course based on
by VSEPR theory) and the fact that it could belong to Dmhpoint group. 0 - H and C = 0 bond moments.

2.10.2 Symmetry and Optical Activity

In Sec. 6.10 of Unit 6 of CHE-01 course, we have explained the concept of optical
activity. A molecule is optically active only if it could exist as separate len-and
rigbt-bandedforms or mirror image isomers. Lactic acid (Fig. 2.21) is an example of
an optically active molecule. From symmetry point of view, we can define optical
acivity. A molecule is optically active only if it cannot be superimposed on its mirror
image through improper rotation. Since a rotation about an axis followed by a
reflection in a perpendicular plane (i.e., improper rotation) converts a right-handed
object to a left-handed object, the presence of Sn axis indicates that a molecule cannot
exist in separate left-and right-handed forms. This implies that any optically active
molecule will not have an axis of improper rotation, Sn. It is important to check
whether a molecule has Snaxis even in an implied way. For example, the molecules in F k 221: k c t k meld: the
len-mnd rlghl-bmndcd lonns
the point group Cnhare not optically active, since these molecules have S,, axis as (mlrror Images).
implied by the presence of both Cn axis and uhplane. All molecules with centre of
symmetry are optically inactive. It is so since any molecule having the inversion centre
possesses S2 ;i is equivalent to C2 followed by uh which is equivalent to S2as explained
in Secs. 2.6 and 2.7.

Evcn ifa molecule possesses only u, then also it is optically inactive since u is equal to
S1[one ;fullrotation qf the molecule by 364 (Cl) through any axis, followed by
reflection across a perpendicular plane]. Thus, fluorochloromethane (Fig. 2.22) which
has u is not optically active.

To sum up, molecules having Improper rotation axes will not be optically active. For
example, lactic acid belongsto Cl and is optically active. Molecules having u (i.e.;S1), i
(i.e., Sz) or any other Snare optically inactive.
Fig, 2.22: o plane In CHLFCl

2.10.3 Spectra and Molecular Symmetry

encloses C. F and C1 .
We can examine the microwave and infrared spectral characteristics of a molecule to
understand the molecular symmetry or vice versa.

We shall see in Unit 3 of this course that only molecules having permanent dipole
moment can give rise to pure rotational (or microwave) spectra. Thus, ohly molecules
belonging to the point groups C, and C, which have permanent dipole moment can
exhibit pure rotational spectra. For example, CO (C,,) and CH3Cl (C*) can exhibit
pure rotational spectra but not C 0 2 (Dmh)and CC&(Td).The former two possess
permanent dipole moment but not the latter two. This again a u l d help us in
confirming the point group classification of a molecule.

InUnits 4 and 5 of this course, we shall see that for a molecule to give rise to
vibrational spectra, one or more vibrations of a molecule must give rise to a dipole
moment change. The vibration spectra could be understood using the symmetry
aspects of a particular vibration of a molecule. The assignment of infrared spectral
frequencies to the specific vibrations causing the absorption c& be made using group
theory., We shall discuss some of the aspects of group theory in the ~ ~ p e n dofi xthis
Bask Conepts and Robtlonal Answer the following SAQs.
sw-
SAQ 10
CI-$C$ has the following symmetry elements:

E, C2 and 2 a,,
a) Identify the point group.
b) Will the molecule show permanent dipole moment?

SAQ 11
Both C02 and CO are linear. Which of the two can exhibit pure rotational spectra?
State the reason.

SAQ 12
1-~romo-1-chloroethane
belongs to Cl point group. Is this molecules optically active?
State the reason.

..........................................................................................................................................................

..........................................................................................................................................................

'2.11 . SUMMARY
In this unit, we have discussed symmetry aspects of molecules. We have explained the

2.12 TERMINAL QUESTIONS

1. (a) Using VSEPR theory, fmd the shape of XeOF4.
Hints : Of the 8 electrons of Xe, 4 are involved in forming four Xe -F bonds;
2 electrons are involved in Xe+O bond which should be considered
like a single covalent bond only. The other two electrons form a lone
pair around Xe.

(b) Draw its shape.

(c) Name the principal axis of XeOF4.

2. Although CHC13has tetrahedral structure, it h& symmetry elements Symmetry of Molecules
(a)
similar to NHY The C- H bond in CHC13is a C3 axis. There are three
a, planes, each plane enclosing C -H bond and one C- CI bond. Identify
the point group of CHCls

(b) Can it have permanent dipole moment?

(c) Can it exhibit pure rotational spectra?
(d) Can it be optically active?
3. (a) [ptcu2- has a square planar structure. State the name of the two proper
axes of symmetry.
(b) Does it have centre of symmetry?
(c) Can it have permanent dipole moment?
4. (a) HBr is a linear molecule. State the name of the principal axis of symmetry
in it.
(b) State its planes of symmetry.
(c) Name its point group.
(d) Can it have permanent dipole moment?
(e) Can it exhibit pure rotational spectra?
5. H20 belongs to Cz, group. Name the symmetry elements in it.
6. (a) For PF5, predict the shape using VSEPR theory.

(b) State any three symmetry elements in it.

(c) Identify its point group.

2.13 ANSWERS

Self Assessment Questions

The central atom phosphorus has three bond pairs and one lone pair. Hence, it
is trigonal pyramidal.
Through drawings it can be established that the equivalent configurations arise
thrice one after the other, and finally the identical configuration.
PC13 has C3 axis.

There are 3 a, planes in PCIY Each a, plane encloses one P-CI bond.
The plane of symmetry in SOCh must pass through sulphur and oxygen atoms
since one atom each is present. The two chlorine atoms must lie on front and
back sides of this plane.
Presence of S6 axis indicates that rotation through 60" followed by reflection in
a perpendicular plane leads to equivalent configuration.
The dipole moment of C6H6is zero, since it has a centre of symmetry.
Using Table 2.3, it can be shown that PC13 belongs to C3, point group.

b) The molecule can have permanent dipole moment, since its point
group (Ch) is one among the C,, groups.
C02 belongs to D, h point group and does not have permanent dipole moment.
Hence, it cannot exhibit pure rotational spectra. CO belongs to C,, point group
DdcCnm#mdb1Cd.tk..l a d has permanent dipole moment. Hence, it can exhibit pure rotational
8- spera.
(12) 1-bromo-1-chloroethaneis optically active, since it does not have S, axis.

Terminal Questions
1. (a) XeOF4 is square pyramidal in shape.

(4 c4

2. (a) q,"
(b) It can ha= permanent dipole moment.
(c) It can exhibit pure r o t a spectra.
(a) It cannot be optically a&.
3. (a) %and C4
(b) It has centre of symmetry.
(c) It cannot have permanent dipole moment,
4. (a) c,
(b)
(4 cam,
(d) It can hare permanent dipole moment.
(e) It can exhibit pure rotational spectra.
5. E, C2and BV.
6. (a) Trigonalbipyramidal
(b) c3.qb*toqand@b
(4 Djb

2.14 APPENDIX

The Basic Aspects of Group Theory

The p u p theory is the mathematical method for dealing with the application of
symmetry concepts to spectroscopyand molecular structure We shall deal with the
following aspects of group theory in this section:
i) The criteria of a p u p
ii) Character table of point groups
iii) Uses of character tables
 The Crite* of Group
. A group is a collection br a a t of elements which should satisfy the five criteria
mentioned below. The elements of a group are related to one another through a
combination process. The elements of a goup may be splmetry opereons of a
molecule or the real numbers (- = to + =, inclusive of fractions). The combination
process may be multiplication or addition. A group should satisfy the following five
criteria:

1. The produd of.two el~llentsof a group gives another element of the group.

If A and B are two elements of a group, then the combination, AB, leads to C,
which is also an element of the group. The combination AB means, B is carried
out f48t and then A The combination AB need not always be equal to BA (BA
means A is carried out first and then B). That is the order of combbation is quite
hprhnt. Those groups for which AB =BA are said to be wmmutativearAbelim
groups; t,in Abelian groups, each element commutes with other elements of the
group.

2. An element combines with itself to form one of the elements of the group.

3. Every group has one element whicb eommotcs with all the elements of the
group to kave them unchanged. This element is called the identity element and
is indicated by the symbol E.

Enmplw
(a) E A - A E - A
) EB-BE-B
4. Every element baa an inverse or reciprocal which also belongs to the group. The
element and the inverse combine to give the identity e/ement.

-pk

1f A-' is the inverse af A and, B-' the inverse of B, we can write

5. Every element of the group obeys the associative law of combination. If A, B

and C arc three elements of a group and the process of combination b
multiplication, then the associative law tells us that

We caa illusbate the criteria of groups using the symmetry operations of Ch,point
goup.

Thc four symmetry operations of Ch,point group, E, C,@),q @z)andu: (yr) r r M y

t h criteria ofgroup. Let us explain the significance of the operations,
Es C,(4,0" Ctz) andu; Q.
\

operations am be understood using the following diagnms ( F IA

~l ) where
o~~too&nn~w~tkhohy&qluatomland2ild(P)thex.ydz
coor ates of oxygen atom are affected by these operations.
BMIC Concern and Rotatlolul
sp.etn

C#) mcuu rotation throu@

lm uouad z-axis.

and u; 6z) operatioas.

P b A1:B, C2(L),q (z)

Note that ,C2 operation is carried out aroundz-axis and it interchanges the positions of
HIand atoms besides changing thex and y coordinates on oxygen atom. You can
observe that the positkss of the two hydrogen atoms and the coordinates of the
oxygen atom remain the same as s result of E operation. But the a, (xr) operation
changes they coordinate of oxygen atom while retaining thex andz coordinates of
oxygen atom and the positions of two hydrogen atoms. r h e operation a: Q results in
the change of positions of two hydrogen atoms and thex coorcihate of the oxygen
atom. Using the rules that define a group, we can construct the following
multiplication table (Table A.l) for Ch,group.

Tk c k m e n u d o p p u t itr Table kl:Multiplication Table for Ch,group

mnrtitutnth Thc ckmentr d the
p u p d i r u r c d in thir armpk uc
tk w m c t r y o p ~ t i o l r rsuch m
refkction, rotation ctc. Thev
ckwau uc aot to k c d d
with rymmctry ckmcntr such m
phac of rprmetly, utk of
rplmetty, etc.
 Note that any particular symmetry operation appears only once in each column or Symmetry o f M o l e c u l g
each row. In order to verify the entries in Table A.l, you must remember the
convention that the operation listed at the top of the table has to be carried out first
followed by the operation listed at the left side. For example, the execution of
operation uv(xt) followedby the operation C2(z) gives rise to u: @). The sequence of
wrying out the operations uv(xt) and C2(z), and the resultant product, ui 012) are
represented by means of curved arrows I and II in Table A.1. The product of
operations q (nt) and C2 (z) can be represented by Eq. A.1.

Eq.A.l can be understood using Fig.A.2; this helps in verifying the first ofthe criteria
of a group stated above.

You can verify the other four criteria of group using the symmetry operations of Chr
group. Note that in Ch, group, the inverse of each element (i.e., symmetry operation) is
' the element itself.
Thw LC2 (z1l-l = c2 (2)

These are characteristicof Ch,group. These relationships along with the fact that
E-' = E should help you in verifying the entries in Table A.l and also the fact that
uv(xz), a;' Q,C2 (2) and E form a group: A matrix is a rectangular array of
numbers or symbols for numbers,
which may be combined with
Next we shall devote our attention towards the formation of character table of Chr other such arrays according to
point group. This could help us in studying some of the applications of group theory. certain rules. You go through
Unit 13 of P M T CourSe or Unit 5
of ME-04 Course for p t t h g an
Character Table of Point Groups elementary idea about matrices.

The symmetry operations of a point group can be represented using a set of matrices.
Each matrix is called a representative. The sum of the diagonal elements of a matrix is
called its character. It is possible to reduce a matrix into smaller matrices known as
krreducible matrices. A set of irreducible matrices corresponding to thesymmetry
operations of a point group is known as irreducible representation. Each irreducible
representation describes the effect of symmetry operations on the directional
properties such as translational coordinates @,y, z ) rotational coordinates (R, 5,R,)
etc. It ispossible to obtain useful information by listing the characters of all possible
irreducible representations of a po$t group in a tablular form known as character
table. The set of character values of each irreducible representation is denoted
by thesymbol r.
B-ic Coa-pb and Rot.tlonal We shall use a simple method to arrive at the character table of Ch,point group and
Slwctm then illustrate its uses. This can be done by seeing the effect of four symmetry
ope,rations of Ch,group on the signs of the lobes ofpx ,py andp, orbitals. If the signs of
the lobes remain the same after performing a symmetry operation, the resulting
change is represented by 1; on the other hand, if a symmetry operation changes the
signs of the lobes, then it is represented by -1. In other words, the value of 1signifies
'
no change in signs of the lobes while a value of -1 signifies a change of sign.

Effect of Symmetry Operations onp, Orbital

The signs of the lobes ofp, orbital remain the same after identity operation (E); so
E can be represented by 1.
X
EPX = 1PX

Y
This can be understood since performance of identity operation means doing nothing.

The signs of the lobes ofpx orbital changes by C2 operation (about the z axis) and
hence, this operation can be represented by - 1.

The signs of the lobes ofpx orbitals remain the same after reflection through uv(xz)
plane while there is a change after reflection through ad &) plane.

0, (MPX = ~ P X

or uv(z)can be represented by 1.
or a: (yz) can be represented,by-1.

The four numbers corresponding to the operations E, C2,uv(=)and a: (yz) onp,

orbital constitute a representation which we shali call rl and denote as follows:

T1 I 1 -1 1 -1 x

Effect of Symmetry Operations on Py Orbital

If wc proceed on similar lines, we can find out the four numbers corresponding to the
four operations of Ch group onp,,orbital and write r2 representation as shown below

c2v E c2 a, (4 ad b) py orbital

72 1 -1 -1 1 Y

In other words, C2 and uV(xz) result in changes of signs of thep,, lobes whereas E and
a: Q cause retention of signs.

Effect of Symmetry Operations onp, Orbital

By similar arguments, we can arrive at the decision that E, C2, uv(xz) and a: (yz) do
not change the signs ofp, orbital. Each of the operations can be denoted by 1 only in
the representation rf

Effect of Symmetry Operations on Quadratic Coordinates

From the columnwise products of rl, r2 andr3, we can get the r values forxy,yz, andxz
as follows:
E c2 a, @) 4 @a Note that
i)r, = r1r2
x (TI) 1 -1 1 -1 ii) r2 = t2r,

Y 1 -1 -1 1 iii) r, 5 rl r,

(~3) 1 1 1 1

The representation (r4) for the operations on xy is different from the representations
corresponding to the operations onx,y or z; but the representations for the operations
onyz and= are r2 and rl, respectively, which are same as for those on y andx.

You try columnwise products such as rl rl or r2 r2 or r3 r for obtaining

2 2
representations corresponding to the effect of the four operations onx ,y and z2. If
you work out correctly, you should be able to prove that all these representations are
the same,viz, r3, which is the representation corresponding to the effect of the four
operations on z.
Basic Concepb and Rotational E C2 0
: bz)
Spectre
x2 ory2 orz2 (r3) 1' 1 1 1

Effect of Symmetry Operations on Rx, R and Rz

Y
. The symbols, Rx ,Ry and R,, denote the rotations around thex - ,y - andz-axes.

The molecule, H20, is inxz plane. The operation E on R, leaves it unchanged. The
operation C2 aroundz-axis does not alter the direction of R, rotation. Hence E and C2
operations on R, can be represented by 1. The operations, uV(xz) and u: @), reverse
the direction ofR, rotation, and hence, these two operations can be represented by-1.

We can-see that the representation corresponding to the effect of operations on R, is

same as r4.

E c
2 UV (4 4 (Yz)
R* 1 1 -1 -1

Similarly the effect of the four symmetry operations on Rx and Ry can be stated
through following representations:
E c2 Ov (4 0; (Y4
Rx 1 -1 -1 1 02)
-1 1 -1 (~1)
% 1

Thus we see that these are only four representations rl, r2, r3 and r4 for C2, group.
There are rules to give names to these representations which are known by the name,
Mulliken notations. We shall not discuss these rules but use MuUiken notations of
B1, B2, A, and A,- for rl, r2, r3 and r4, respectively.

These four representations can be represented in a table called the character table of
the C2vgroup (Table A.2). Also, we would have arrived at the same table, had we
started with the matrix representation of symmetry operati~nsand proceeded to
obtain the characters of irreducible representations.

The four rows of Table A.2 represent the sets of characters for the four irreducible
representations of Ch, group.
 Table k2: Character Table of Cz, Symmetry o f Molecules

1 -1 -1 I Y,p Rx Al repmentation is said to be

totally symmetric representation
since any directional property
The value under E represents the dimensions of a representation. In Ch, group, d l the belonging to representation of
four representations are one-dimensional and in each case, E = 1.such Ch point group does not suffer
representations are called non-degenerate representations. In these representations, sign change due to ofthe
the application of a symmetry operation does not interconvert one orbital into symmetry operations.
another; for instance,px ,pyandp, belong to different representations, namely
B1, B2and 4.Also, 4 representation is said to be totally symmetric representation of
Chrpoint group since the character value is 1for all the four symmetry operations.

The formation of character table for C3, point group is more complicated and hence
we shall only give its character table without much explanation (Table A.3).

Table A.3: Character Table for CSvGroup

The Mulliken notation of E is used for a representation, if the character value of 2 is

observed for the identity operation, E. The representation E is two dimensional; this
meansx andy, R, and$ ,xz a n d p etc. which are all bracketed together are
interconverted by a symmetry operation; i.e., those bracketed together are degenerate
and hence have same energy.

Uses of Character Tables

We can make use of character tables to solve specific problems such as those given
below:

1. Selection rules regarding the allowed transitions between energy levels in

(atomic and) molecular spectra.
2. Symmetry species of vibrational modes in m.olecules.
3. Hybridisation schemes in molecules of specific geometry. I

The second one will be explained in Units 5 and 6 and we shall not be discussing the .
third of the above. Let us now see how selection rules for transitions in the molecular
spectra can be derived using character tables.

Selection Rules for the Allowed Spectral Transitions

The selection rules for the spectroscopic transitions throw light on the type of initial .
and final energy states for allowed spectral transitions. The selection rules specify the
conditions for the allowed transitions in terms of changes in quantum numbers. Let us
examine the first of the above two.
Basic Concepts and Rotational 1.The Type of Initial and Final Energy States for Allowed Spectral Transitions
Spectra
Let us first see how to decide whether a particular spectral transition is allowed or not.
va
Let and Vb be the wave functions of two energy states a and b, and M, the transition
dipole moment operator for which the components are M, ,MYand M,. The transition
dipole momentp during the transitions between states a and b can be defined as

where dr is the volume element. The three components of transition dipole moment
Ol,,py andp,) can be defined in' terms of the components of dipole moment operator
(M, ,My and M,) along the three axes as follows:

But M, = ex,My = eyandM, = ez ...(A.6)

where e is the electronic charge, andx,y andz are the cartesian coordinates.
MI, My and M,a= the
Combining Eqs. A.3 to A.6,
components of the transition
dipole moment operator (M)
whercas,pI , ~ ( ~ a n d p , a the
xt
components of transition dipole
moment. '

The intensity of a transition is

proportional to the squarr of
the transition dipole moment.
Dipole moment k a molecular For a spectral transition to occur from the state, a to b, atleast one of the components
property. Don't confuse the ofp (vlz,ppp,, orpJ should be.a finite quantity (i.e., should be nonzero). On the
permanent dipole moment of a other hand, if all the components Or, ,py o r p 3 are zero, then the spectral transition is
molecule with the term, totally symmetry forbidden.
transition dipole moment.
Transition dipole moment Furtherp, ,py orp, will be finite (i.e., nonzero), only if the product of the symmetry
comes into play when a
molecule interacts with a species of the functions, 1V, andvb, and the transition moment operator, M,
radiation and is related to the
probability of a transition taking
vb vb va vb
My or M, (i.e., M, %, My or M, 1 ~ ,is) totally symmetric; for example, the
place from one energy state to product must belong to Al representation for the molecular point group Cm Since
another. M,, M andM, transform likex,y andz coordinates, we can state that the transition
Y
moment integral will be nonzero, if the product of the s mmetry species of the
H
functions, Vb and% and the coordinates (x,y,z) is tota y symmetric. Further, it can be
shown that the symmetry species of the product, Vbx Va, Vby Va or ?lo z va will be
totally symmetric, if the symmetry species of the product sf t i e functions Vb and tV, is
the same as that ofx,y andz coordinates.
For example, let us examine whether the transition from the molecular state with
symmetry of wave function (va ) as Al to the state with symmetry of wave function (vb)
as B1, is allowed for the molecules of C2" group. From Table A.2, we know that 5 y and
z belong to B1, B2 andAl representations, respectively. Let us see whether any of the
va
three products, q b xv,, v b y ty, orVbz belongs to Al representation.

i) Representation of the product, f i x 1V,

Function Symmetry Characters in four columns
species E c
2 0, (4 0; 014
Vb Bl 1 -1 1 -1
You can see that the qbqa product has the same representation asx. So Symmetry of Molecules

qbqax (or q b xqa) is totally symmetric.

ii) Representation of the product, qiy

Function Symmetry Characters in four columns
species E c2 a, (4 0; 62)
Vb Bl 1 -1 1 -1

We can see that the symmetry species of the product, qb ,is different from that of
they coordinate.

Hence, the product q b y tV, does not belong to Al representation.

ill) Representation of the product, qbz %

Function Symmetry Characters in four columns
species E C2 UV (z) uV1(vz)

Note that the transition moment

has thrce components,
p x , p y a n d p , . Ifonly onc,say.x
Again qb belongs to B1 representation which is different from that of the component is different from zero,
z-coordinate. Hence, the product, qbq; z also does not belong to totally. symmetric
. then the transition is said to be
representation. polarized in the x-direction. If two
of the componcnts, say,px andp,
Hence, we see that Vbxty, belong to A1 representation although q b y% and z va vb are different from zero, then thc
transition is said to be polarized in
do not. Hence the* component of the transition dipole moment is non-zero. t h e 9 plane. If all the componcnts
Therefore, we concluhe that the transition Al- B1 is allowed and is polarized in @ , , p , a n d ~ ) are different from
thex direction. By similar procedure, it can be shown that (i) the transitions

- -
zero, then the transition is fully
B2---+ 4 and B1- 4 are allowed, the former being polarized in thex direction allowed. Similarly, if all the three
and the latter in they direction and (ii) Al 4 and B1 B2 transitions are components arc zcro, thcn
transition is totally forbidden and
not allowed. its intensity is zero.

Specific Selection Rules

Further, a detailed study of the transition dipole moment leads to specific selection
rules which state the conditions for the allowed transitions in terms of changes in
quantum numbers. In Units 3 and 4, we shaU study selection rules specific to rotation
and vibration spectra.

Next, let us discuss the method of identifying point groups of molecules.

Identification of Point Groups

It is possible to find out the point group of a molecule by knowing its shape and
symmetry elements and, by using Table A.4.
Basic Cenecpta and Table A.4: Flow Chart for Identifying Point Groups.
Rotational spectra
1) Is the molecule linear?
Yes No
1
2) Does the molecule have i? 3) Does the molecule'have two or more C,

Yes
I No
I
axes of order greater than 2 ?

Yes

4) Does the dolecule have i?

'I I

+,
5) Docs the molecule have Cs?

. .I
6) Does the molecule have C,,axis ?

Yes 1 No

7) Corresponding to the order (n) of principal 13) Does the molecule have' d
axis.(C,), does the molecule have nC2 axes yes 1
perpendiculer to the principal axis?
I
cs I
14) Does the molecule have i?

I
Yes I No
I
Dn h 10) Does the molecule haveah ?
Yes No
I I

I
1 1) Docs the molecule have n uv ?
9) Does the molecule haven ud?
I I
~ d s NO
I.
Dnd
I
Dn . ,+A
Yes

'
12) Does the molecule have Snaxis
of even order greater than 2 ?
Note that the questions in the flow chart given above are numbered. This is done for Symmetry of Molecular
referring to the questions which are relevant for identifying the point group of a
particular molecule.
$i

For identifying the point groups, the following steps would be quite useful:
Step i) Find out the shape of the molecule; this can be done using Sec. 2.2 of this To predict the shape of the
unit. molecule, you may use Scc. 2.2 of
this unit and Scc. 3.7 of Unit 3 of
Step ii) List the symmetry elements in the molecule. CHE-Ol (Atoms and Mokeules)
COUTSC.
\
Step iii) Mark those questions from Table A.4 which are relevant to the symmetry
elements of the molecule under consideration. Write down the answers
and the inference. The answer to the last question gives the point group
of the molecule.

Let us examine a few examples in the light of the steps mentioned above:

I H2
Step i) H2 molecule has linear shape.

Step ii) H2 has the following symmetry elements:

E, 2C,, =C2 (perpendicular to C,), ah, =av, 2 S, and i

Step iii) The questions of Table A.4 relevant to this molecule are given below
alongwith the answers: Note that in Step (ii), we have
mentioned many symmetry
1. The molecule is linear (Proceed to question 2). elements for H~ molecule. B U ~in
Step (iii), all these symmetry
2. Hz has i. The answer to this question indicates that the point goup elemenma* not used for arriving
at the point group of the
of Hz is Dmh. molecule. Thus, the point p u p
ot a molecule can be found out by
In short, all linear molecules with i such as acetylene, and homonuclear diatomic using a few symmetry elements
onty. While writing step (ui),
molecules belong to Dm,,point group. follow Table A.4 carefulty.

I1 HCl
Step i) HCl molecule has linear shape.
Step ii) HCl has the following symmetry elements:
E, 2C, and = a,

Step iii) The questions of Table A.4 relevant to this molecule are given below
along with the answers:
. 1. The molecule is linear (Proceed to question 2). - -

2. HC1 does not have i. Hence, the point group of HCl is C, .

In each of the examples I t o N,we
Similarly, all linear molecules without i such as heteronuclear diatomic molecules mention under step (iii) only
relevant question numbers from
belong to C, point group. Table A.4 along with answers.
Thus, in Example I11 for H20, the
relevant question numbers arc 1,
111 H20 3.6.7.10 and 11. T h e "ye&' o r
"no" part of the answer for each
question can be inferred from the
Step i) H20 molecule has angular shape. word in bold type. T h e answer t o
the last question gives the point
Step ii) H20 has the following symmetry elements: group of the molecule.

E, 2 uv and C2.
Basic Coaecpts sad Robtl~nsl Step iii) The questions of Table A.4 relevant to this molecule are given below
Spectra along with the answers:

1. The molecule is not linear (Proceed to question 3).

3. The molecule does not have two or more Cn axes of order greater
than 2 (Proceed to question 6).
6. The molecule has C2 axis. (Proceed to question 7).

7. The molecule does not have two C2 axes perpendicular to the

principal axis (C2). (Proceed to question 10).

10. The molecule d y s not have ah(Proceed to question 11).

11. The molecule has 2a,The last answer indicates that the point
group of H20 is Chr

SO2 is another example belonging to Ch, point group.

Step i) NH3 molecule has trigonal pyramdal shape.

Step ii) NH3 has the following symmetry elements:

E, 2 C3 and 3 av

Step iii) The questions of Table A.4 relevant to this molecule are given below
along with the answers:
1. The molecule is not linear (Proceed to question 3).
3. The molecule does not have two or more Cn axes of order greater
than 2 (Proceed to question 6).
6. The molecule has C3 axis (Proceed to question 7).

7. The molecule does not have three C2 axes perpendicular to C3 axis

(Proceed to question 10).
10. The molecule.does not have ah(Proceed to question 11).

11. The molecule has 3 a,. Hence, the molecule belongs to C3, point
group.

As an exercise, you try to identify the point groups of BF3 and C6H6.