UNIT 3 ROTATIONAL SPECTRA

Structure
3.1 Introduction
Objectives
3.2 Molecular Motion and Energy
33 Rotational Spectrum of a Rigid Diatomic Molecule
3.4 Applications of Study of Rotational Spectra
3.5 Non-Rigid Rotors
3.6 Rotational Spectra of Polyatomic Molecules
3.7 Population of Rotational Energy Levels and the Intensities of Spectral Lines
3.8 Summary
3.9 Terminal Questions
3.10 Answers

3.1 INTRODUCTION
From this unit onwards we shall study the interaction of electromagnetic radiation with
an assembly of molecules rather than atoms, as has been done in the first unit of this
Block. This interaction will result in the so called molecular spectra of compounds.
Just like we extracted information about the structure of atoms from the atomic
spectra, we shall try to find out what information can be obtained from the molecular
spectrum regarding the structure and the behaviour of a molecule.

It will be seen that absorption or emission of electromagnetic radiation in different

regions, corresponding to different amounts of energy, would cause various types of
changes in the molecule. Thus, the spectra in each region would give a definite and
specific piece of information about the molecule. For instance, when the molecule is
subjected LO radiations in the microwave region, we get information about the
rotational properties of the molecule which in turn gives the values of molecular
parameters like bond length.

On the other hand, molecular spectrum in the infrared region is related to the
vibrational properties of the molecule. About vibrational spectra, you will study in
Units 4 and 5 of Block 2. Since each region of spectrum requires a separate source of
characteristic radiation, sample preparation and recording technique, you will study
about them separately in Unit 9 of Block 3.

In this unit, we will start our discussion with the concept of motion leading to the idea
of moment of inertia associated with a rotating body. On the basis of the moment of
r n ~ r t ~~iiolccule\
~i, a\ Irii~ar.\?rnriictrlc top, asymmetric top and
~ v r l lhe clnss~fic~i
spherical top molecules. We will then explain the rotational spectra of rigid linear
molecules in detail. We will also see what happens when a molecule is not rigid? We
will explain briefly the rotational spectra of simple polyatomic molecules and intensity
of spectral lines.

Objectives
After studying this unit, you should be able to:

a define the moment of inertia,

a discuss the rotational spectra of rigid linear diatomic and triatomic molecules,
a give applications of study of rotational spectra,
Buic Concepts md kotational a explain the effect of isotopic substitution and non-rigidity on the rotational
Spectra
spectra of a molecule,
a classify various molecules according to their values of moment of inertia,
a discuss the rotational spectra of simple polyatomic moleoules, and
a relate the intensity of spectral lines with the population of a rotational level.

3.2 MOLECULAR MOTION AND ENERGY

The understanding of molecular motions help in the interpretation of molecular
spectra. When we talk about molecular motions, there are various possibilities. When
we want to specify the position of a body in space, we have to specify the number of
degrees offreedom it possesses. The number of degrees of freedom is related to the
number of independent coordinates required to specify the position of the body in
space. Fcr example, for a single particle we need three Cartesian coordinatesx,y andz
to specify its position. Hence, it is said to have three degrees of freedom. Thus, for a
molecule having N atoms, the total number of degrees of freedom is 3 N .

For a single particle, only one type of motion is possible which is called translational
motion. Hence, we can say that a single particle possesses three degrees of
translational freedom.

But what about translational motion of molecules? A molecule contains two or more
than two atoms. Since the atoms in a molecule are joined together, the molecule as a
whole will show translatory motion and the atoms will not move independently. The
translational motion of a molecule can be described in terms of the centre of mass.
The centre of mass is the point where the whole mass can be considered to be
concentrated. Thus, we can specify three coordinates for the centre of mass and say
that it has three degrees of freedom, similar to a single particle. The translational
motion of centre of mass of a molecule (non-linear) is shown in Fig. 3.1.

A molecule can store energy by Flg. 3.1: Translational motion of centre of mass of a nonlinear molecule.
way of molecular motions.
For a polyatomic molecule having N atoms, ( 3 N - 3 ) degrees of freedom still remain.
These can be attributed to internal motions such as rotation and vibrations.

Let us now know more about rotational motion. The simplest case of rotation is that of
a particle about a fmed point, as shown in Fig. 3.2.
 Fig. 3.2: Rot:~llonot a parllclc about a tbred polat.
The rotational kinetic energy of this particle having mass m and velocity v can be
expressed as

(@
Q
1 P2
Ek = - mv2 =
2
- wherep = rnv is the momentum of the particle
2rn
...(3.1) 'C
hr
0 A0 P
The velocity of this particle could be expressed as the distance travelled by it divided r(t)
by the time taken. For one revolution, we can say that 9 &'

=- L' - - --h r
distance
time t
... (3.2)
where t is the time taken for one revolution and is also known asperiod. For circular motion if a paiticle P
traverces an angle A 8 in time At, _
1 the arc PQ represented as A s it8
Also t=
frequency (j) ...(3.3) given by the following relation:

Substituting the value oft from E.q. 3.3 into Eq.3.2, we get r . A 8 = AS

Dividing by A t on both the sides,

v = 2nr.f (3.4)
--, are get

-
Replacing v in Eq. 3.1 by its value from Eq.3.4, we can write
When At 0 . we can write

The terms in the above equation can be rearranged as given below:

... (3.6) or ,mr-,

where a, is the angular velocity
The quantity nt? of the above eq-.lationis called the nloment of inertia and is and v is the linear velocity. The,.
angular velocity, a, is defined as
represented by I. The term 2 j ie. known as the angular velocity and is denoted by o. the number of radians of angle
swept in unit time.
de
Thus, we can rewrite Eq.3.6 as It is given by - where dB is the
dt '
angle traversed in dt time. It is
Ek = 1/21 02 , ...(3-7) expressed in terms of radians rer-'.

On comparing Eqs.3.1 and 3.7, wc can say that in the equation for rotational motion
(i.e., Eq. 3.7), moment of inertia is the equivalent of mass as used in Eq.3.1. Also in
Eq.3.7, angular velocity ( w ) is used in place of linear velocity (v) used in Eq.3.1.
I

3.3 ROTATIONAL SPECTRUM OF A RIGID DIATOMIC

MOLECULE
-..
Let us now apply the above ideas to the rotation of a diatomic molecule. We will first
assume that this diatomic molecule is a rigid body. This means that the distance
between the atoms, i.e. the bond length does r~otchange during the r a t i o n . In other
Basic Cmecptr md Rdatlonal tvords, vibrational movement is not taking place during rotation. We are also assuming
Spectra that the centre of mass of the molecule is fixed. Hence, there is no translational motion
of the molecule. No real molecule can be called an ideally rigid body. But many molecules
[nay be considered as rigid because their vibrational motion is small. Let us now focus our
attention on Fig. 3.3 which depicts the rotation of a rigid diatomic molecule.

Note that the axis about a x i s of rotation

which the rotation takes
plaa, is perpendicular to the
axis of symmetry of the
molecule.

I I symmetry

((11 (b)
Flg. 3.3:(a) A rlgld dlatomlc molecule.
(b) RohUoo of a rigld diatomic molecule.
When such a molecule rotates, it rotates about an axis passing through its centre of
mass(('hl! The centre of mass is shown by the point 0.For such a system,the centre of
mass is such a point for which the following condition is satisfied:

ml r1 = m2r2
We can rearrange Eq. 3.8 as follows

Using the characteristics of proportions, Eq.3.9 can be written as

We also know that the bond length or the distance between twoatoms. r-,isequal to the
sum of rl and r2.Thus, we can write

Substituting r = rl + r,- from Eq. 3.12 into Eq.3.11, we get

On similar lines, we can get

by starting from Eq.3.8 and rearranging it as

Why do not you try Terminal Question 1and check it.

Let us now write the energy of this system using Eq3.7.

You can imagine this molecule a:;a two particle system (Compare Figs. 3.2 and 3.3). Rotational Spectra
Heie, you can see that two particles (atoms hav& masses nt,- and k 2 ) are rotating
Note that the moment of inertia for
about the point o. Thus, the rotational kinetic energy, Ekof this system will be the sum , , < .

of the Ekvalues of both the particles. So, we can write I = m# and for a diatomic molecule
!.", :',,;l,<t.',\\i,',,I I' \L\;,!L' ..:
as 1 = ml 4 + 4.
mz We can qxtend
(3.16)
,.. this argument and generalise it for
.
~ o l.v a t o m i cmolecules as follows.
For a polyatomic m o ~ e c u kthe ,
The angular velocities of the two masses m, and m2 will be equal because of the moment of inertia about a particula
- . of the molecule. Hence,
rigidity axk is given by the sum of moments
due t o various nuclei about that cuh
w1= 0 2 ...(3.17) 4
i r . , I = L mi where ri is the
i
perpendicular distance of the
Let this angular velocity be w . So, we can rewrite Eq.3.16 as nucleus of mass mi from the air

where I ii the moment of inertia 11fthe diatomic molecule.

The terms rl and r2 can be eliminated,from Eq. 3.18 by using the values of rl and r2
from Eqs. 3.13 and 3.14, respectively, as given below:

=A [m1mV + m2mY
2 (m, + ,n2)2 (ml + m d 2

Remember that we have earlier

defined I as &.
...(3.19)
Comparing Eq. 3.19 with Eq. 3.18, we can say that

ml m2
Thus, I= r:i
("fl+ "2)
Here, m1 m2 can be denoted byp wbich is known as the reduced mass.
(ml + m2)

Thus, we can write

1=p2 ...(3.22)
 B*Canc*rdmd'oolrl Thus, the idea of using reduced mass is to mathematically simplify the rotation of a twoparticle
Spntra system into that of a oneparticle problem. In other words, we have replaced the two
niasses ml and m2 by a single massp. You must have also realised that similarlywe
have also replaced the two distances rl and r2 by r.

At this stage, we have come to a point where we can deal with the rotation of a
diatomic molecule having masses ml and m2 in terms of the rotation of a single
particle of massp having a distance r from the origin.

Let us now reconsider Eq.3.18 which says

This equation isalright as per &e classical mechanics approach. But when we apply
quantum mechanical approach to the molecule, certain restrictions appear on the
rotational energy.

D o not confuse the L used in Eq. Eq. 3.18 can be expressed in terms of angular momentum L which can be defined as
3.24 witb that used in unit 1. Herr,
L F p m e n t a the angular L =Iw ...(3.23)
momentum of the molecule
undergoing end to end rotation
about the centre of m a s wherpas SubstitutingL for I w in Eq.3.18, we get
in unit 1,it was used to denote the
angular momentum of the L~
ekctmn inan atom. E , = 51 7
Since the angular momentum is quantised, it can be expressed in terms of the
rotational quantum number, J, as given below:

The rrstriction on the value of J

comer from quantum mechanics.
where J can takeiralues 0,1,& 3...

Substitutingthe above value of L in Eq.3.24, we get

,

The above equation gives the rotational energy of a molecule. The energy can also be
v.
expressed in terms of wave number, The energies as expressed in terms of i; are
referred to as krm values and are denoted by F (J ). The SI unit of a term value is m-I
, but they are usually expressed in cm'l.
h
We li,~\cL I F C ~tl = - 111 Eq 3 27

Thus,

The term -can be represe&ed by a constant B which is known as rotaUonal

&?IC
constant, Hence, 9 3 - 2 7can be written as

v = B J ( J + 1)

Thus, when J = 1, v = 2B cm"

J = & ;=6~cm-l

J = 3, 5 = 1 2 cm-'
~
and so on.
The corresponding energy levels are depicted in Fig.3.4
-

But we are more interested in knowing the difference between these energy levels so
that we can know the radiation of what frequency or wavenumber is absorbed or
emitted'when a molecule changes from one rotational level to the other. Thus, we can
write the difference between two rotational levels-as follows.
AE= E -E where J' is the final rotational level and./
h TI k~~ is the initial rotational level.

The for the above energy change can be given as follows:

v,,.,,= B [J'(J ' + 1 ) - J(./ + 1 )]
From Fig. 3.4, we can see that the energy difference between the successive energy
levels is 2B, 48,68,8B, 10B and so on. The spectral lines originating from these
transitions will appear as shown in Fig. 3.5.

Flg. 3.5: The transitions between the varlolur rolatlonal levels and spectre1 Ihm mbhg
rrom these trunsitlons.
B;lsic Cwcepts and Rotational If you carefully see Fig. 3.5, we will notice that these spectral lines are equally spaced
Spcctra
and there is a constant difference of 2B between the successive lines.
For a molecule to show rotational spectrum, the following requirements should be met.
i) The first condition which a molecule should satisfy for showing rotational
spectra is that it should possess a permanent dipole moment. This is because a
rotating dipole produces an oscillating electric field which interacts with the
oscillating field of the radiation.
ii) There is a further restriction on rotational transitions for molecules having
permanent dipole moment. The selection rule for linear molecule is A J = 2 1.
So transitions could be from rotational levels having J = 0 -,J = 1;
J =l-,J=2;J=2-,J=3;J=3-J=4 andsoon and in the reverse order
also.

Another factor which governs the intensity of rotational lines is the population of the
initial or ground state. You will study about this in Sec. 3.7.

The Condition for the Occurrence of Pure Rotation Spectra

In the Appendix of Unit 2, we have mentioned the applications of character tables.
One of the applications lies in determining whether a spectral transition could
occur from an energy state a to the energy state b. For such a transition to occur, at
least one of the components of the transition dipole moment, p, which is equal to
$ tyb M ty,, must have a non-zero value. You may be aware that tyb and tya refer to
the wave functions of the energy states, b and a, whereas M is the dipole moment
operator. In case of pure rotation spectra, it means that at least ope of the three
components of transition dipole moment, tc,,py or p, in x, y and z directions must
have a non zero value in order that the molecule absorbs in the microwave region.
p, py and p, are related to M, My and M, which are the components of the dipole
moment operator M as given below:

P ~ = $ v ~ ~ ~ ~ ...~(A.1)~ ~

py = $ u ~ ~ ~ ~ u ~ ~ ~ ,..~ (A.2)
pZ= $VJbMzva ...(A.3)
Note that p (bold type) stands
for transition dipole moment
whereasp (Roman type) refers
Also M, My and M, are related to the permanent dipole moment , p , of a rotor and
to the permanent dipole the polar coordinates, 8 and @ ,as per Eqs. A.4 to A.6. For understanding the
moment.Alsot(,~(yandp~are resolution of the dipole moment operator M in terms of M,, MYand M, as per
the componentsof transition
dipole moment inx,y and z Eqs. A.4 to A.6 and Fig. A.l, you are advised to go through Eq. 2.54 of Unit 2 of
directions. CHE-01 ('Atoms and Molecules' Course) where the relationship between the
spherical polar coordinates and the cartesian coordinates is given.
Mx = p sinOcos@ ...(A.4)
My =psinOsin@ ...(AS)

A
M, = p cos8 ...(A.6)
If a molecule lacks permanent dipole moment (i.e., p = 0), then M, My and M, and
hence,p,, pyandp, are zero as per Eqs. A.l to A.6. For a molecule having zero dipole
@ moment, all the three components of transition dipole moment are thus equal to zero. .
1 ,,*,
As> result of t h ~ s amolecule
, with zero dipole moment cannot give rise to pure
*. rotation spectra. In other words, for a molecule to absorb in the microwave region,
it must have permanent dipole moment. Insub-Sec. 2.10, of the last unit, we have
mentioned that only molecules belonging to the groups C,' (Cl and CJ and
Fig. A.1: 'I'ransformaUon of C,,, (C2,,C,,. .. ..Cr,) and Cs may have permanent dipole moment. Now you can
earteshn lo spherical
pohr coordlm(Cs
understand as to why HBr, CO and OCS (all of C,, point group) can exhibit pure
rotation spectra but H2 and C02 of Dmhpoint group) cannot.
SAQ 1 --Spacbr

What is the effect of decrease in the moment of inertia on the energy of the rotational
level?

............................................................................................................................................................
SAQ 2

What is the necessary condition for a molecule to show rotational spectrum?

3.4 APPLICATIONS OF STUDY OF ROTATIONAL

SPECTRA
(i) Determination of moment of inertia and bond length
From the last section, you know about the relationship between the energy (or
wavenumber) of radiation absorbed or emitted, required for the change of rotational
level and the moment of inertia. You can now think of the reverse process of what we
have learnt above. If we determine the frequency of radiation absorbed or emitted
requiredsforthe change of a particular rotational level, we can relate it to the value of
B, the rotational constant. Once B is determined, we can calculate the moment of
The value of rotational constant, B
inertia using the expression B = .-.The value of moment of inertia SO obtained of am. ~ o l r ~obtained
l ~
872 IC from their rotational spectrum is
can be used to give the value of r, the bond length if we know the reduced mass of the given below:
system. One such example is illustrated below:
Molecule ~/em-'

The transition from J = 0 to J ' = 1for HC1 takes place at V = 21.18 cm-l. What is the co 1.93128
bond length of 1H35 C1 ? HP 20.90
HBr 8.4648
HCI 1059
Let us follow the steps we have listed above. HI 6.426
KC1 0.1286

Thus,
-v = 2 B cm-' (from Eq. 3.29)

Also, I= - h
an2 BC

Now I=p#
To know r, from the above equation, we have to first calculate p as shown below:
@)
13c160
Thus,

= 1.275 x lr1°m
r = 127.5 pm
Another application of the study of rotational spectra is in the determination of the
mass of a particular isotope or isotopic abundance of a particular isotope.

You know that isotopes differ from each other in atomic mass. If we consider a
particular molecule and another substituted molecule having an isotope of a particular
atom substituted, there will be a difference in the masses of these two molecules. For
example, if we consider 12c16and
as compared to 12c160.
higher mass isotope, i.e. 13c160
0 13C160, there is an increase in the mass of
Then, the reduced mass of the molecule having
.
in this case, is more than the 12c160This would
13 16
lead to a higher value of I for C 0 which in turn indicates a lower value for
rotational constant, B for this molecule. The experimental values of rotational
constants of 12c16and 0 13c160 are as given below:

= B = 1.92118 cm"
Rotational constant for 12c160

= B ' = 1.83669 cm-'

Rotational constant for 13c160

If we carefully examine the expression B = - ,we conclude that the terms h, x, c

slt2Ic
are all constant and B is inversely proportional to I. Thus, we can write

-3-
B h -
&I'c (here I and I ' represent the moment of inertia
B slt21c' h for 12c160 and 13c160, respectively.

Thus, -B= - = LI=' 1 . 0 4 6

B I P

(the bond length r of the molecule does

not change on isotopic substitution)

From the above equation, we know the ratio of p ' top. Thus, if we knowp, we can
calculate p'.

Hence p ' = 1.046 p ... (3.31)

 We h o w that atomic mass of '60 = 15.9994 and that of =C = 12.00 b t d o d m

and

Expressing the Eq.3.31 in terms of atomic masses a6 expressed in Eq.3.32 and 333,
we get

On solving the above equation, we o b h the value of m,,c =13;0007 which is the
precise value of mass of *C isotope and is in agreement with the value obtained by
othcr methods. Before we close our d i s c d o n on the determination of atomic mass of
an isotope, we would also like to focus your attention on the appearance of the
rotational spectra after isotopic substitutioq You have studiid ebwa in case of
'k160 that substitution oPa heavier isotope leads to a deaeasc in the value of
rotational constant. Since the value of B is related to the spacing of spectral linu in the
rotational spectrum, a lower value of B' indicates smaller acpatatioa between the
rotational levels and also in spedral lines This is shown in Pi& 3.6.

Till now we based our discussions on the rigid diatomic molecules. In the next sectipn,
you will study what happens whet1 we are dealing with a non-rigid molecule. Before
going to the next section, answer SAQ 3 given below to check your understanding
about the above section.

( From the rotational spectra of "NO and " ~ 0 , i twas found that 5- 1.0361Where B

and B ' are rotational constants for 1 4 ~and

0 I S ~ 0 respectively.
, Calculate the atomic
mass of "N if the masses of ' 4 and~ Oare 14.004 and 15.!WM, ri!spectively.
 3.5 NON-RIGID ROTORS
The rigid rotors we considered before present an ideal case and actually when a
molecule rotates, its atoms experience a centrifugal force. Since the bonds are elastic
to some extent, when a nob-rigid molecule rotates, the centrifugal force leads to the
stretchiig of the bonds. This stretching leads to an increase in the bond length and
hence an increase in the moment of inertia. As a result of this, there is a decrease in
the separation between the rotational energy levels and also in the spectral lines. see
Figs.3.7 and 3.8.

v=4B -320
ZB
v=2B v = ~ B - ~ 28-4D
D 6-
Rigid Rotor Non-rigid Rotor
Rigid Nanrigid
Fig. 3.8: Energy level diagram for the rigid and non-rigid rotators. The spectral lines arising from the
PI& 3.7: EUul of ce~lruwgd transitions are indicated below the energy level diagrams.

On (he enem levelr This effect is taken care of if we write the v as given below:
of a dhtomlc rotor.
V=BJ(J+ I ) - D J ~ ( J + I ) ~ ,.. (3.34)
where D is the centrifugal distortion constant and is given by the following equation.

The value of D is obtained from the spectral results and is always very much less than
B. The spectra of non-rigid molecules will show a decrease in the spacing between
rotational levels and in spectral lines similar to the one shown in Fig. 3.6 but here the
decrease will be comparatively much smaller.
In b e next section, you will study about the rotational spectra of polyatomic molecules.

3.6 ROTATIONAL SPECTRA OF POLYATOMIC

MOLECULES
Till now, we focussed our attention on the simple case of linear diatomic molecules.
The rotation of a polyatomic molecule is quite complex as compared to the diatomic
molecules considered above. The rotation of a polyatomic moleale could be
simplified and understood in a better way if we consider components cf the rotation
about the three principal axes. Thus, a three dimensional molecule will have three
moments of inertia about the three axes (x,y, z). You may remember that in the
previous case of a diatomic molecule, we considered the rotation about an axis
perpendicular to the axis of symmetry of the molecule. But actually, the rotation of the
diatomic molecule could be about all the three axes (x,y andz) as shown below:
 i
x&,z
Note that the moment of inertia
about the molecular axis is zero and
the moment of inertia about the
.k.: to the
CM x ~ CM y ' ~ z other two asisarc
molecular axes perpendicular
identical
Hence, only one numerical value of
x Ioccurs for a linear moltcule and
x
the energy is defined by only one
(a) (b) (4 quantum number, I.

Flg. 3.9 :'Rotetlonof a dlatomlc molecnk about centre of mass

(a) about x axis (b) about y axis (c) about zaxis.

Let the moments of inertia for the above rotations be represented by I s , It and I,, In case of polyatomic molecules
when the rotation in three
respectively. Since the rotations as shown iu part (a) and (b) are equivalent, we can say dimemions is possible, kinetic
IB = I,%.In part (c), the moment of inertia about the bond axis (y-axis) has a very slnall energy of rotation (Et) can be
given as
value as compared to Is and Ic and w6 can use an approximation that I, = 0. The 1 1 1
E t = -2I A 3A +jlB";+-i~3c
small value of I,%could be attributed due to the differences in the masses and the radii
... (3.36)
of the nucleus and the electrons.
Similar to Eq.3.24, we can write
You know that most of the mass of the molecule is concentrated in the nuclei of its
atoms in a very small space. But the electrons having very less mass occupy relatively
large space. Therefore, the electrons contribute a major share to the moment of
inertia'along the axis of symmetry because only they will be contributing to the
motion. The total moment of inertia (both due to electrons and nucleus) is very where LA = I,, 'u*
small. Since the energy of the rotational levels is proportional to +,the energy of the
rotational levels corresponding to rotation about the symmetry axis (Fig. 3.9(c)) will be
very-very high as compared to that of the rotational levels for rotations shown in Figs.
3.9(a) and (b). Thus,these rotational levels will not contribute to the rotational kP&a
Here, the magnitude of total
and the value of moment of inertia used in Eq. 3.26 could be either of IB or Ic because angular momentum is given as
,

both of them are equal. follows:

With this background in our mind, let us shift our attention to polyatomic molecules.
Polyatomic molecules can be classified into various groups according to their values of Thus for linear molcculeswhere
moments of inertia along the three principal axes. Such a classification is given below I\ = 0, 1:q. 3 3 7 hecoines as follows:
in Table 3.1.

Table 3.1 :Various Classes of Polyatomic Molecules.

Moments of Inertia Type of Rotor Examples Rotational

Constant
IB =Ic,I&
=0 Linear CO, HCI, OCS A=a,B=C
1~-I< = I,,, Spherical top C&, SF6 A=B=C

> <
I+$/IM Prolate A>B=C
Symmetrical top
CUIF. cH3c1
11 >Iu=I( Oblate Bcl3,Gd-b A=B>C
bthtlc Asymmetric top C M E h ,Hz0 A t B t C

About the linear systems, you have already studied in detail for diatomic molecules.
Similarly, we can treat linear triatomic and other linear polyatomic molecules.

Let us study the case of a triatomic molecule OCS. Here also we will assume that it is a
rigid molecule. If you see the structure of OCS shown in Fig. 3.10, you can find that
there are two bond lengths, C-O and C S . But we have one value for the moment of
inertia which cannot give two values of bond distances. This problem can be solved by
using isotopic substitution as follows.
Basic Coaccptr m d Rotational .-
Sptcb8

3.10: OCSI molecule.

Let the masses of 0 , C and S be represented by m, m, and m,, respectively. Also let
the distances of the atoms 0,C and S from the centre of mass (G) be represented as
to,r, andr,, respectively. The centre of mass (G) will be such that

The moment of inertia of this system (I)is given by the following equation.

We can express ro and r, by the following expressions (see Fig. .3.10).

and .r,=rcr-rc ...(3.41)

We can substitute the above values of ro and r, from Eqs. 3.40 and 3.41 into Eq.3.38 to
yield the following expression.

Bringing all the terms containingr, on one side, we &XI write

I, (m, + m, + m& = mar,-morco

If we represent mo + m, + m, , the total mass by M,the above equation becomes as
given below I 4 #

r p -mrrcr-motm ...(3.42)
Similarly, we can express Eq. 339 for I in terms of toandr, as given below:

I = mo (rm + rJ2 + mc( +ma (r,-rd2

= 111 r
0 CO
2 2
+ lllOrc ~ 52
+ 2 1 1 l ~ , r+~11rcrC +vtSrA +nisr: -211tsrcsrc -

Rearrangiog, we get

I =m,e +me$ + m , 4 + 2r,(morm-m,r& + m0&+ ma& ...(3.43)

=~~+2~(m,r~~-m,r~+m~&+m,& ...(3.44)
80
Substituting value of r, from Eq. 3.42 in0 the above equation, we get W s o Y b .

r . n r ( " . " i m o r ~ ) 2 + r ~ r ~ ~ ~ o .r ~ )~ o ~ c o - m s r ~ + mQ .ow r~u b+apnnion.

fo~~owing e ~~msp l ~
ifkdtothr

...(3.45)
You auyrcmcmba that boa8
Eq. 3.45 is the one on which we will further focus our discussion. It contains the two - ~~~~~a~~~~~~~
unknown distances rcoand r,. Suppose-we carry out an isotopic substitution in the out.
molecule. i.e., we substitute ''0 in place of ''0 and then record the rotational
spectra, The equation for moment of inertia (I') of this new molecule thus becomes as
given below:

where m,' represents the mass of the isotope of oxygen. Now, we have twk equations
[Eqs. 3.45 and 3.461 and we can evaluate two unknowns r, and r, provided we know
the other parameters in these equations.

Next category of molecules is that of spherical top. These molecules have all the three
moments of inertia as identical. As far as the value of rotational energy is concerned, it
can be obtained by using any one of the above values of moment of inertia. These
molecules behave similiu to linear molecules as far as their rotation k concerned The
same equation as obtained for linear molecules can be applied to give the value of
EL or B. But because these molecules, being symmetric in nature, do not poaoess any
dipole moment; Thus, these molecules do not show pure rotational spectra.

We will next consider symmetric top molecules. You are aware that in these
molecules, two moments of inertia are equal but the third one is different. When this
third moment of inertia is less than the other two equal moments of inertia, the
molecules are known as prolate molecules. On the other hand, when the third
moment of inertia is greater than the other two moments of inertia, then the
molecules are known to be of oblate type. Both these type of molecules are shown
belowinFSg.3.11.

'1
, "1 '.
benzene. ChH,,

I boron trilluoride, BF1

inethyl lluoride. CH3F
-
311: W8(. a d +l.b qmmdrlc m o l e d a

\gain, in these molecules first we consider that the molecules are rigid and derive the
:nergy expression by solving the Schriidinger equation. The following equation is
bbtained by using the above method.
Basic Cmcepts md RoWlolul
Spectra -
"JS = *
E~y=81(~+1)+G(-~)~2cm-1

h
We will not go into the details where, B =-
of arriving at Eq.3.47. It is valid
for prolate mo~ecules. &I+
For oblate molecules, . \

F= BJ(J+ 1)- (B - c ) ~ ~ c m - '

Here, J is the total angular momentum and K is the component of angular momentum
about the unique aris. The unique axis along the C-X bond of C%X molecule is
Unique axis is also known as shown in Fig.3.1 I .Obviously the values of K will be smaller than or equal to J. Thus,K
TOP axis. can take the following values. \

So, K can take 21 + 1values.

From the above equation, you can see that K can have negative values as well. The
+ ve and -ve values are associated with the clockwise and anticlockwise rotation
about the symmetry axis: When K = 0, it means that there is no rotation about the
symmetry axis or unique axis.
Eq. 3.50 permits determination of
only one rotational constant.
Hence the complete geometry of a Eq. 3.47 shows that the rotational energy depends upon the K~terms. So the anticlock
symmetric top molecule cannot be
determined by using this single wise or clockwise rotation (i.e., the +ve and -ve,wdues of K) will have same value for
value of B obtained from spectra.
In such a case. isotop~c
K~or energy. Thus, the levels corresponding to and an will be degenerate.
substitution is used in structure
determination. The selection rules for th'e rotation of such molecules are
Thus, centrifugal distortion leads
to a slight separation o f the
components of I.
The selection rule of A K comes from the fact that there is no dipole moment about
the symmetry axis (rotation about which is represented by K),hence electromagnetic
radiation cannot interact with the rotation about this axis. Hence, it is expressed as
AK=O.

If we apply the above selection rules to Eq. 3.47, we get

- -
v(J+~,K)-V(J,K) = [B(J+ l ) ( J + 2) + (A-B)K~I-[(BJ(J+ 1) + (A-B@I
= 28 (1 + 1) cm'l ...(3.50)
where J = 0, 1, 2...............

You can see that K is not reflected in the final equation for rotation and Eq. 3.50 is
similar to expression for ti obtained for the rotation of linear mol&ules.

Similar to the case of linear molecules, the centrifugal distortions due to non-rigid
nature of real molecules are taken care of by incorporating an additional term in the
energy expression as given below in Eq. 3.51:

Thus, we could take the case of symmetric top molecules to be similar to that of linear
molecules. The same procedure can be used for calculating B and I and bond lengths
for symmetric top-molecules as done earlier for linear molecules. But here, there will
 be a diffcrcnce in the obser\,cd spectrum for .\ynlmctrictop molecules as far as the Rolallonal Spectra
splitting of rotational lines is concerned. Since each value ofJ is associated with 21 + 1
values of K and the levels corresponding to + K and -K being degenerate. This leads to
the fact that the spectral line assuciated with a particular level will be split into J + 1
components. Thus,,thc following splitting pattern bc observed.
-
whcn, J K L! (from Eq. 3.51)

Thus, the spectrunl obtilincd will look likc as shown below in Fig. 3.12.

:i;,,:TI
!
K=2

328 + (A*)

K=2
; J=4

K=2 \a /'+
,
'128 4 (A*)
J=4,K=O
ZOB P3
J=3,K=l K=2
J=2 fa*4W-a)
'=I
J=3,K=O
,a-x' i
J=2,K=1 a /
68 +(A*)
J=2. K=O 68 ,,/*';=I,K= 1 48
Yl + (A*)
,

Plg. 3.12: (a) Rotntbnal energy Ievcb mf pmlmlc cymmetrlc lop molecules
(b) Spllttlng of relational c p u h d lines for symmelrlc top molecules

Remember that no such splitting was observed for linear molecules. In other words, by
studying the spectra, you can know whether a certain molecule is of linear type or of
symmetrical top type.

The analysis of rotational spectra of last class of molecules, i.e., Asymmetric top
molecules is quite complex and a general expression for energy cannot be written for ~~~~~~e~~~~ ;!"
'L
' ~~~~
them. Each molecule of this class requires individual treatment. In this course, we will ,
,,ll,, of(J +
not go into the details of analysis of rotational spectra for this kind of molecules. lines.

In the next section, yoli will study about the intensity of spectral lines.

3.7 POPULATION OF ROTATIONAL ENERGY LEVELS

AND THE INTENSITIES OF SPECTRAL LINES
According to the selection rule, all those transitions where A J = 2 1 are possible. It
has been shown by calculations that the probability of all such transitions is the same.
However, this does not mean that all the transitions will have the same intensity.
Although the chances of a molecule going fiom J = 0 to J = 1is the same as
J = 2 to J = 3, yet the intensity of the two lines may differ. This is so because the total
number of molecules initially present in J = 0 will be different from the molecules
present in J = 2. The larger the number of molecules present in a particular state, the
WC-ccpbmd Ra.(ioml IarprwiII be the chances of transitions to thc next state and hence greater will be the
spcctn intensity.

The population of thc cncrgy state dcpends on (1) Boltzmann distribution and (2) the
dcgeneracy of thc state.

Boltzmann distribution can be expressed as,

whcrc, NJ = number of molecules in any state

N,, = number of molecules in the lowest level, i.e.,
/=o
E j = energy differcnce between the two statcs
k = Bobzmann constant
T = tempcraturc in Kelvin
Eq. 3.52 can be rcwrittcn as,

One thing is clear from Eqs. 3.52 and 3.53 thirt the ~lclllulaticlnof ilil'lkrcnt slates kccps
on decreasing in an exponential manner as we kccl~on incrcasing tlic / valuc.

Howcver, there is another factor-the degeneracy of the slntc tvhich will affcct the
population. We shall not discuss the origin and numhcr of such dcgcncrate statcs,
except to emphasise that degeneracy of a state incrcascs thc ~ w l ~ ~ l a tof
i oanpnrtieular
energy state.

The net result of the two factors is that the population rises to a nlmimum and then
decreases as / value increases. The band with maximum intensity is given by,

SAQ 4
Calculate the relative population of first two rotational energy levels for HCl at
300K.Use B = 10.49 cm-'

3.8 SUMMARY
In this unit, you learnt about various types of energies associated with m e r e n t kind of
molecular motions. Rotational motion was the one in which were interested in. In this
context, the terms moment of inertia and angular velocity were explained. Then, the
rotation of a rigid diatomic molecule was discussed in detail. The energy levels
associated with such molecules were considered which in turn were related to the
observed rotational spectra.

The applications of rotational spectra study were highlighted. The case of non-rigid
molecules was also explained. This was followed by the discussion of rotational spectra
of polyatomic molecules. In this class, linear, spherical and symmetric top molecules Rotatioari Spectra
were discussed.

Lastly, the relationship between the intensity of rotational spectral lines with
population of rotational levels was described.

3.9 TERMINAL QUESTIONS

m1r
1. Using m lrl = m 2r2, derive r2 =
(m,+ m2)'
2. Calculate the energy in terms of G of the energy level corresponding t o J = 7.

3. What is the selection rule for a rigid diatomic molecule to show rotational
spectrum?
4. Which of the following molecules will show rotational spectra?
O = C = O , HF,N2

5. If the rotational constant ior H 3 S is~10.

~59 cm-l, what is the value of
rotational constant for 2~ 3 5 ~ ~ ?
Use ~06 x 1
mass of 3 S =~58. ( kg ~ ~ ~
mass of 2~ = 3.344 x kg
mass of 'H = 1.673 x kg

3.10 ANSWERS
1. From Eq. 3.26, a decrease, in moment of inertia will lead to an increase in the
energy of the rotational level.
2. It should possess a permanent dipole moment.

= 5.007~

For J = 0 , -N= IJ
No
Further Reading
1. J.RDyer, Application of Absorption Spectroscopy of Organic Compounds,
Eastern Economy Edition, Prentice-Hall of India PvtLtd.

2.- -D.RWilliams and Ian Fleming, Spectroscopic Methods in Organic Chemigtry.

Tata Mc Graw Hill Publishing Co. Ltd. 4thEd.

3. C.N Banwell, Fundamentals of Molecular Spectroscopy, 3rd Ed,

Tata McGraw Hill Publishing Co.'Ltd.
NOTES