BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 14

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Rotational Spectroscopy
or
Microwave Spectroscopy

Rotational spectroscopy
Spectroscopy in the microwave region is concerned with the study of
rotating molecules.

When a particular molecule rotate, the range of rotational

frequencies (corresponding to diff. between rotational levels) is of the
order of frequencies: 8x1010 - 4x1011 Hz, (: 0.75 - 3.75 mm) This falls
in the microwave region of the electromagnetic spectrum.
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Pure Rotational spectroscopy

At least two atoms bonded together and tumbling in space
constitute a rotational motion.
Rotation of linear molecules is easy to
understand, however the rotation of 3D body is
quite complex.

A rotating molecule could be approximated to a

rigid rotor (not elastic), and thus the rotational
energy is quantized.
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RIGID ROTOR-Quantized Levels

If such a rotating rigid rotor (molecule) possess
a permanent dipole moment, then such
rotations
will
provide
a
oscillating
electromagnetic field that will interact will the
electromagnetic field of the incident light
(microwave light) and microwave light
stimulates rotational translations.

The rotating molecule will get excited by absorbing

energy from incident light, equivalent to the
difference between specific rotational energy levels.
Analysis of the transmitted light results in a
spectra.
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Selection Rules: Pure Rotational Transitions

Gross selection rule: Molecule must be polar (possess a

permanent dipole moment)
Specific selection rule: J =1
J ; rotational quantum number

Practically applicable to samples in Gas phase. In solids or liquids

the rotational motion is usually quenched due to collisions.
Long Sample path lengths required.
Homonuclear diatomic molecules do not have a pure rotational spectrum.
Polar molecules are rotationally active: HCl, NH3, H2O, CH3Cl
Non polar molecules are rotationally inactive: CH4, SF6, CO2, H2, C6H6
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Diatomic molecule as Linear Rigid Rotor

A diatomic molecule may be thought of as two atoms held together with a

massless, rigid rod (Linear rigid rotator model).

Ia

The moment of inertia of the molecule about

the centre of mass is given by:

I = m1r12 +m2r22 = Ia (along an axis of rotation)

Where: r1 + r2 = r

m1m2 2
r r2
m1 m2

Other Rotations could be thought of considering

the rotational components about perpendicular
Ic directions through centre of gravity.

Ib
Energy levels are given by EJ = hBJ(J+1)

Ia = Ib & Ic = 0

J = 0,1,2,3,. is the rotational quantum no.

B = /4 = h/82I
B (in Hz) is called the rotational constant
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Diatomic molecule as Linear Rigid Rotor

When a rigid unsymmetrical linear
molecule changes its quantum
number from J to J+1, the change in
rotational energy of the molecule is:
E = EJ+1 EJ
= [hB(J+1)(J+2)] [hBJ(J+1)]
E = 2hB(J+1) = hJ
Rotational Transition frequencies
J 2B(J+1)
In spectra, series of absorption
lines at J =2B(J+1) appears
with J = 0,1,2,3. [2B, 4B, 6B..]

Why this
pattern
2B 4B 6B 8B 10B

Separation 2B from which can find I

and hence bond length

J = 0 J = 1
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J = 1 J = 2
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Relative Intensities of rotation spectral lines

For Linear Rigid rotor, Intensity depends upon two factors:

1. Population of rotating molecules in the rotational level: Since the

difference between the rotational levels is of the small order, thus
many levels are occupied to different extent at ordinary temperatures.
Greater initial state population gives stronger spectral lines. This
population depends upon temperature, T. (Boltzmann distribution)

2. Degeneracy of rotational levels: A given state in a level may have low

population, however the total population in the energy level containing
large number of states may be quite high.
Each level J is (2J+1) degenerate population is greater for higher J states.
PJ
EJ
hBJ(J 1)
(2 J 1)exp (2 J 1)exp

P0
kT

kT
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Relative Intensities of rotation spectral lines

1
2

kT 1
J m ax.

2hB 2
Maximally Populated Level

For example,
Linear molecule, O=C=S,
Jmax = 22

The thermal equilibrium relative populations

of the rotational energy levels of a linear rotor

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Other types of molecules

Symmetric tops (or symmetic rotors)
Oblate symmetric tops
Prolate symmetric tops

Spherical tops (or spherical rotors)

Asymmetric tops
The energies of rotational levels for these molecules are given by
modified equations and there are extra specific selection rules which
govern that out of these which of them are rotationally active or not.

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Raman Spectroscopy
..A Brief Introduction

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Raman Spectroscopy
In 1928, Professor Sir C. V. Raman observed that wavelength of a
small fraction of radiation scattered by certain molecules differ from
that of the incident beam.

Laser 4880

The shift in the wavelength depends upon the

chemical structure of the molecules responsible
for scattering.
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Raman Scattering
Raman Spectra was obtained by irradiating a sample with a
powerful laser source (NARROW FREQUENCY BAND) of
monochromatic radiation (either visible or infra red ).

During irradiation, the spectrum of the scattered radiation is

measured with a spectrometer.

Raman Spectroscopy is the

measure
of
intensity
and
wavelength of the scattered light
from molecules generated by laser
sources.

Raman Spectrometer
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Polarizibility:
Basis of Raman Spectroscopy
Molecular Polarizability refers to momentary distortion of the
electrons distributed around the bond. The induced dipole moment
generated on applying a static electric field as a result of separation
of positive nuclei and negative elelctrons makes a molecule polarized.
Induced dipole moment (Polarizability) can be generated in any
direction by varying the direction in which the electric field is applied.

extend

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Basic Principle of Raman Spectroscopy

Light is scattered by the sample at various angles by momentary

absorption to virtual state and reemission.
If the light is elastically scattered, emissions occur at the same energy
(Rayleigh radiation). While a small portion of light gets inelastic scattered.
Stokes radiation scattered radiation of lower frequency than incident
radiation, energy transfer to molecule.
Anti-Stokes radiation scattered radiation of higher frequency than incident
radiation, energy transfer from molecule.

energy absorbed by
molecule from photon
of light not quantized

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Polarizibility: Classical Explanation for

Raman Spectroscopy
When such a polarized molecule is subjected to a beam of
radiations (of certain frequency, ), the induced dipole
undergoes oscillations of frequency ( ) equal to the
frequency of the incident radiation.
Such an oscillating dipole emits radiations of its own
oscillation frequency, (Rayleigh radiation).
If in addition, the molecule undergoes some internal motion,
such as vibration (or rotation), which changes the polarizibility
periodically, then scattered light will lose energy equal to the
difference in vibrational (rotational) energy levels (Stokes lines).
Sometimes, the scattered light will gain energy by interacting
with an excited molecule (Anti-Stokes lines).
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Academic Counseling Cell

CELEBRATES

"TEACHERS (AND STUDENTS) DAY"

(A fun interaction between faculty and students)
Date: 5th September 2016, Monday
Time: 5:00 PM to 6:00 PM
Venue: Rotunda
All Faculty, and Students are invited !
Refreshment will be served.