Knowledge of Spectroscopy

1 1
Rotational Spectroscopy
(Chem-411F)

1 2
 What is Microwave Radiation?

qMicrowaves are a form of electromagnetic

radiation with wavelength between 1 cm 100 µm,
3 × 1010 – 3 × 1012 Hz.
1 3
Do you use microwave in practical life?

• Cooking

• Communication
Ø Radio
Ø Satellite
Ø RADAR

1 4
 World War-II

Pearl Harbor attack,

7 December, 1941
By Japan

1 5
 What is Rotational spectrum?

☛A technique that monitors the absorption or

emission of radiation in the microwave region
of the spectrum.
Ø Rotational spectra-due to change
in the rotational energy of the molecule.
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Why is rotational motion of
interest to CHEMISTS?

Energy can be taken up by a

molecule in any of several ways.

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 What is Chemists interest to study
Microwave?

Analysis of Molecular and atomic structure

How?
1 8
 Rotation of Molecules

Key parameter : Moments of inertia

Definition

xi is the perpendicular distance of the atom i from the axis of rotation.

Rotational properties can

be expressed by moment
of Inertia
1 9
Why Moment of Inertia is Important?

1 10
 What is Chemists interest to study Microwave?

Analysis of Molecular and atomic structure

How?
‘I ’depends on-
(1)The masses of the atoms present
(2) The molecular geometry

Ø Bond lengths 1 Ø Bond angles 11

 Rotation of Molecules

vThe principal axis of rotation:

The direction in the plane of the paper passing
through the center of the gravity of the molecule
and perpendicular to the axis A.

The axis perpendicular to both A and C axis The molecular axis

and passing through the center of gravity
of the molecule.

1 12
 Classification of Molecules

i. Linear molecule: Molecules are arranged in a straight line

q The three direction of rotation may be taken as:

a) About the bond axis
b) End –over -End rotation in the plane of paper,
c) End-over-End rotation at right angles to the plane.

Linear molecule: IB = IC IA= 0

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 Why IA is Zero for linear molecule?

As the nuclei of the atom which gives the main

contribution to the mass are situated in the axis A, the
moment of inertia about this axis is approximately zero.
1 14
 Classification of Molecules
(ii) Symmetric top molecule:

Main rotation
axis

• The C–F bond axis having a three fold axis of symmetry is the
a axis, has the smallest moment of inertia

• Two mutually perpendicular axis b & c lie in a plane

perpendicular to the a- axis. Therefore, IB = IC
• A molecule spinning about the a axis resembles a
spinning top and hence the name1 symmetric top. 15
 Symmetric top molecule:

(a) Prolate molecule:

( IB = IC >IA )

✪Rotation about the principal axis has the smallest

moment of Inertia and is chosen as a axis.

B and c axis are perpendicular

1
to a axis 16
 Symmetric top molecule:
(b) Oblate molecule:
(IB = IC < IA )

The principal axis is chosen as C axis,

has the smallest moment of Inertia.
1 17
 Spherical top:
vWhen a molecule has all three moments of
inertia identical, it is called spherical tops.

IA = IB = IC

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 Asymmetric top:
A molecules with three different moments of inertia
is known as an asymmetric –top Molecule:
e.g.: H2O, CH3OH, CH2CHCl, NO2 etc.
The majority of the molecules belongs to this group.

IA ≠ IB ≠ IC

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Classification of Molecules

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 Rotational Spectroscopy

qSpectroscopy in the microwave region is concerned

with the study of rotating molecules.

Rotational transitions are promoted by Microwave

region. How?

Microwave interactions
1 21
 How a rotating molecule interact
with Microwave?

If the frequencies of the field and rotation

are equal, the rotor will absorb from the
electric field. 1 22
 Molecular requirements
for rotational spectra:
(I) Only molecules that have a permanent dipole moment
can absorb or emit electromagnetic radiation in such
transition.

Example: In the rotation of HCl, fluctuation seen to be exactly

similar to the fluctuating electric field of radiation.

Ø Thus interaction can occur, energy can

be absorbed or emitted and the rotation
gives rise to a spectra. 1 23
Which type molecule does not show rotational
spectrum and why?

1 24
Home work: Which of the following molecules
would show a microwave spectrum?

N2, CO2, OCS, H2O,

CH2=CH2, C6H6 H2, HCl,
CH4, CH3Cl, CH2Cl2, H2,
NO, N2O, CH4 , CS2, HCl,
Br2

1 25
Are rotational energy levels quantized?

Planck suggests that radiation

(light, energy) canonly come in
quantized packets that are of size
hν.

Whether changes in the rotational energy can

lead to absorption, or emission of radiation and
if so, what molecular property can be deduce
from a study of the frequencies of radiation
emitted or absorbed. 1 26
 Diatomic molecule
(Rigid rotator?)

Molecules undergo simultaneous

rotation and vibration.

A treatment that assumes that the molecular dimensions

are independent of molecular vibrations and undisturbed
by molecular rotation is known as the rigid rotor
approximation.
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 Diatomic molecule
(Rigid rotator?)
Classical treatment:
Length of rigid bar, ro = r1 + r2

The moment of inertia,

I = m1r12 + m2r22
𝐼 = 𝜇𝑟!"

Energy of a body rotating about an

axis a is-
# # " # 2
Ekinetic = " 𝜇𝑣 =" 𝜇𝑟! 𝜔 = "I𝜔
2 2

q Kinetic energy is dependent on the moment of inertia

and on the angular velocity. 1 28
 Solution of Schrodinger Equation:

Schrodinger equation for a rigid rotator:

V?

The potential energy term V has been taken zero

as r is fixed.
The solution of rigid rotor gives the energy eigen values.
Rotational energy level is given by;
"!
𝐸! = ! 𝐽(𝐽 + 1) J= 0, 1, 2, 3, ..
#$ %
where J is rotational quantum number
1 29
Rotational energy level in wavenumbers (cm-1)

B is the rotational constant

The difference between the two levels

J= 0, 1, 2, 3, ..

This equation gives whole spectrum to

be expected from such a molecule.
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 Allowed rotational levels

Energy level are

1
not equally spaced 31
 Rotational energy levels and transition

qFor J=1, the rotational energy

is 𝜀𝟏 = 2B and a rotating
molecule has its
lowest angular momentum

q For increasing J values,

𝜀𝑱 𝐦𝐚𝐲 𝐡𝐚𝐯𝐞 𝐧𝐨 𝐥𝐢𝐦𝐢𝐭
𝐭𝐨 𝐭𝐡𝐞 𝐫𝐨𝐭𝐚𝐭𝐢𝐨𝐧𝐚𝐥 𝐞𝐧𝐞𝐫𝐠𝐲

q Step wise raising of the

rotational energy results
in an absorption spectrum
consisting of lines as
2B, 4B, 6B……. cm-1
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Learning points:

Ø The value of B can be deduced from

the spacing between the observed
spectral line.

Ø The moment of Inertial as well as

internuclear distance of the diatomic
molecule can be calculate.

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 Application:
Gillium et al. have measured the first line in the rotational
Spectrum of CO as 3.84235 cm-1.
(a) Calculate Rotational constant
(b) Calculate the moment of Inertia.
(c) Calculate reduced mass.
(d) Estimate the bond length.
(e) Find the rotational energy for first transition.

Hints:
#
a) B= "3.84235 cm-1
&
b) I ='(!)* cm-1= 14.56 10-47 kg m2
c) µ = 11.38365 × 10-27 kg
+
d) r = , = 1.131 Aº.
2 (e)

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The separation of
rotational energy levels
(in small molecules)

about 10−23 J
about 0.01 kJ mol -1
Vibrational energy levels
about 10 kJ mol-1
electronic energy levels
about 103 kJ mol−1).

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 Selection Rule

Quantum mechanics: Energy levels are quantized.

Transition can occur from a particular level to its immediately neighbor.

Schrodinger equation shows that, we need

only consider transition in which J changes
one unit- all other transitions being
spectroscopically forbidden. Such a result is
called a selection rule,

Selection rule: ΔJ = ± 1
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 Intensity of spectral line
q Is a molecule have more or less chance of
making the transition J=0 ➙ J=1 than the
J=1 ➙ J = 2 ?

q For the transition other than ∆J = ±1

(which are forbidden), the transition
probability is zero. (quantum mechanics)

q And the probability of all changes with ∆J

= ±1 is almost the same.

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 Intensity of spectral line
q The probability of all changes with ∆J = ±1 is
almost the same.

q All the spectral lines will be equally intense?

Which is correct?

or

𝜗 1 𝜗 38
 Intensity of spectral line
q In normal gas sample, there will be different numbers of
molecule in each level therefore different total number of
molecule will carry out transition between the various
levels.

q Since the intrinsic probabilities are identical, the line

intensities will be directly proportional to the initial
numbers of molecule in each level.
q The first factor governing the population of the level
is the Boltzmann distribution

q The second factor governing the population of the

levels is the possibility of degeneracy
1 in the energy states
39 .
 First factor : Population

How NJ varies with J

The number in any higher state is given by

Ø There are almost as many molecules in the

J=1 state, at equilibrium, as in the J=0.
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 Relation of J with B

Ø The more rapid decrease of Nj /No with

increasing J and with larger B
1 41
1 42
 Second factor: Possibility of
degeneracy
Relation between kinetic energy and angular velocity.
Ekinetic = I𝜔2,
P = I 𝜔, 𝐏 = 2𝐸𝐼
(P angular momentum, vector quantity)
"!
𝐸𝑛𝑒𝑟𝑔𝑦 𝑒𝑥𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛: 𝐸! = 𝐽(𝐽 + 1) J= 0, 1, 2, 3,
#$ ! %
"!
2𝐼𝐸! = 𝐽(𝐽 + 1) ! ,
&$
"
P= 𝐽(𝐽 + 1) , P= 𝐽(𝐽 + 1) units
'$

v P is quantized like E
1 43
 Intensity of spectral line
Degeneracy, J=1

Three degenerate orientations of the rotational

angular momentum vector for a molecule1 with J=1 44
 Intensity of spectral line
v Each level is J(J+1) fold degenerate

J= 2, P = 6
J= 3, P = 2 3

1 45
 Intensity of spectral line
v The total relative population at an Energy Ej
will plainly be: Population∝ (2J+1)exp(-EJ/KT)

v Population raises to a maximum and then diminishes

Ø The number of degenerate level is increase rapidly with J
although the molecular population in each level is
1 46
decrease exponentially.
 Intensity of spectral line

On differentiating

Ø Line intensity ∝ population of rotational level

Ø Transition between very low and very high J
values will have small intensities
Ø The intensity will be a maximum at or near the
J value given the eq for maximum population.
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Intensity of spectral line

1 48
 Which is correct?

or

𝜗 𝜗
Home work:
Q1. Make a population versus J value diagram for HCl at
𝟐𝟓𝒐 C and 𝟏𝟓𝟎𝟎𝒐 C.

Q2.The intensity of J=0➝J=1 is often not the most intense

rotational line. Why?
1 49
 The effect of Isotopic Substitution

However Mass change alter the moment

of inertia, and B value for the molecule

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1 52
The effect of Isotopic Substitution

1 53
1 54
The effect of Isotopic Substitution

1 55
1 56
The Non-rigid rotator
The difference between the two levels

J= 0, 1, 2, 3, ..

Is a Chemical BOND RIGID?

1 58
The Non-rigid rotator
1 61
1 62