CY 1051 : Introduction to spectroscopic methods

BE/BS/EP/ PH/NA students Ranga Rao G, Tel.4226

Classes : MON (10 am), TUE (9 am) and WED (8 am) Email: grrao@iitm.ac.in
Classroom : CRC 102

13 Jan – 24 April 2020

Total number of students : 114 (including AE/CE/CS/EE/ED/ME)

Teacher : Prof. G. Ranga Rao, Department of Chemistry

Google Hangouts class

14-04-2020 @ 9 am

9840871968

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 Vibrational Raman Spectroscopy

Google Hangouts class

14-04-2020 @ 9 am
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 Vibrational Raman Spectroscopy

When a sample is irradiated with an intense monochromatic light source (usually a

laser), most of the radiation is scattered by the sample at the same wavelength as
that of the incoming laser radiation in a process known as Rayleigh scattering
(unchanged wavelength, elastic scattering).

However, a small proportion of the incoming light – approximately one photon out
of a million – is scattered at a wavelength that is shifted from the original laser
wavelength. This is known as Raman scattering or inelastic scattering.

A small amount of radiation scattered by a gas, liquid, or solid is of

increased or decreased wavelength (or wavenumber).
This light phenomena of inelastic scattering (change of wavelength)
is known as Raman Effect.
It is a very weak effect : only 1 in 107 photos is Raman scattered.
C. V. Raman, ‘‘A Change of Wave-length in Light Scattering,’’ Nature 121 (1928), 619.

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 Raman spectra then

Raman spectrum now

All the vibrational modes of
CCl4 are Raman active,
so Stokes and anti-Stokes
peaks are observed

Stokes radiation : h  E
Anti-Stokes radiation : h  E

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 Banwell book, Ch.4
Inelastic (Raman) scattering

Stokes’ radiation is more intense.

Anti-Stokes lines are appreciably less intense than the corresponding Stokes lines.
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 Classical theory of Raman effect : molecular polarizability
Electric field of the radiation   experienced by each molecule,
E  E0 sin 2 t
Induced dipole undergoes oscillations of frequency  ,
   E   E0 sin 2 t
This oscillating dipole (molecule) emits radiation of same frequency   Rayleigh scattering
OR
The molecule can undergo some internal motion (vibration or rotation),
which can change the polarizability periodically.
This oscillating dipole will be superimposed by vibrational or rotational oscillation.
If vibration changes the polarizability,    0   sin 2 vibt
 0 : equilibrium polarizability Distortion of electron
cloud during vibration of
d
 : rate of change of polarizability with vibration,  a diatomic and the
d variation of polarizability
    E   0   sin 2 vibt  E0 sin 2 t

Expand it using sin A sin B 

1
2
cos  A  B   cos  A  B 
    0 E0 sin 2 t   E0 cos 2   vib  t  cos 2   vib  t
1
2
  exciting frequency stokes' Raman anti-stokes' Raman
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 Rotational Raman: Linear molecules (polarizability tensor is anisotropic,    

J  2 ....related to the symmetry

of the polarizability ellipsoid

EJ  BJ  J  1 cm 1 J  0,1, 2,...
E  EJ  2  EJ  B  4 J  6  cm 1
J : rotational quantum no. in the lower state
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Rotational energy levels of a diatomic and rotational Raman spectrum
Pure rotational Raman spectra
(Read : Banwell section 4.2.1, page 105)
Banwell page 106

EJ  BJ  J  1 cm 1 J  0,1, 2,...
J  0, 2 only
J  0 ....Rayleigh scattering
J  2 stokes
J  2 anti-stokes
E  EJ  2  EJ  B  4 J  6  cm 1
J : rotational quantum no. in the lower state

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When we consider the spectrum of a pure rotational spectrum, with different
states identified by the rotational quantum number J, allowed transitions follow
the selection rule ΔJ = ±1, i.e. only one unit (positive or negative) changes.

When we consider the pure rotational Raman spectrum (i.e. polarizability changes
purely due to molecular rotations), the relevant selection rules are ΔJ = 0, ±2,
i.e. ΔJ = 1 is no longer followed for these transitions.

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Polarizability changes due to molecular rotations in water and chloroform
Banwell book, page 104

Polarizability is different along three axes and

three ellipsoidal axes are also different in H2O.

H2S or SO2 would have similar shaped ellipsoid

but different dimensions.

Polarizability of ellipsoid for chloroform is greater

across the symmetry axis, the minor axis of the
ellipsoid in this direction.

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 Raman & IR : comparison

• Both Raman and IR spectra result due to changes in vibration modes of

molecules.
• Only those vibration modes which result in change in the dipole moment of
a module are IR active
• And those vibration modes that result in change in polarizability are
Raman active.
• IR and Raman activities are related to symmetry of molecules
• Rule of mutual exclusion which states that for a molecule having a centre
of symmetry the Raman active vibrations are IR inactive and vice versa.
• This rule is not applicable to molecules having no centre of symmetry and
in such cases vibrations may be both Raman as well as IR active.

Example : N2O Is this N-N-O or N-O-N?

N2O (nitrous oxide) is a linear molecule with many similarities to CO2 (with
less symmetry).
1298.3 cm-1 596.3 cm-1 2282.2 cm-1

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 • Raman spectra result from scattering of light by vibrating molecules
whereas IR spectra result from light absorption by vibrating molecules

• Raman activity results from change of polarizability of a molecule

whereas IR activity results from changing dipole moment

• A monochromatic light beam of high intensity laser can be used in UV,

visible or IR regions in Raman measurements whereas in IR
spectroscopy the range is limited to IR frequencies

Homonuclear diatomic molcuels (O2, H2 etc) : IR and microwave inactive

but they do give rotational Raman spectra.

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 Vibrational Raman Spectroscopy : classical treatment
Number of peaks related to degrees of freedom
 DoF  3N  6 (bent ) OR 3 N  5 (linear ) for N atoms
1 k 1 k
  Hz  cm 1
2  2 c 
 Selection rules related to symmetry
Rule of thumb: symmetric  Raman active, asymmetric  IR active

Raman

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 Polarizability of molecule
 , polarizability of molecule, is related to the mobility of electrons
(under applied radiation field in the present case)

For atoms, same distortion is obtained for filed in any direction.

Polarizability is isotropic.

For many molecules, polarizability depends on direction of applied field,

e.g. H-H is esaier to distort along the bond than perpendicular to the bond.
Polarizability is anisotropic.

For a molecule to exhibit a pure-rotational Raman spectrum, the polarizability

must be anisotropic; that is, the polarizability ellipsoid must not be a sphere.
A spherical top has a spherical polarizability ellipsoid and so gives
no pure rotational Raman spectrum.
Molecules that give rotational Raman spectra : F2 , C2H4 , C6H6

Pure-rotaitonal Raman spectrum of a polyatomic molecule provides information

on the moments of inertia, hence allowing a structural determination.

Variation of  with direction is described by polarizability tensor.

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Changes in polarizability ellipsoid of CO2 during its vibrations   E
The extent of ellipsoid
measures the reciprocal of .
d
 0 at   0;  Raman active
d

   0 at   0
d
and  0,  Raman inactive
d

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Changes in polarizability ellipsoid of H2O during its 3 vibrations
  E

Raman

The extent of ellipsoid

measures the reciprocal of .
d
 0 at   0;  Raman active
d

There are changes in polarizability

ellipsoid in all three vibrations of H2O
…all Raman active

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 Vibrational Raman spectra (Read : Banwell section 4.3.4 page 113)
2
 1  1
Ev   v   e   v    e xe cm 1 v= 0,1,2,...
 2  2
xe  anharmonicity constant ;  e is the equilibrium vib. frequency in cm 1
Selection rule : v = 0,  1,  2..... as in IR
Raman transition energies :
1. v  0  v  1, v = +1 ...considerable intensity
 1  1
2
 1 1
2

E fundamental   v   e   v    e xe    e     e xe   1  2 xe  e cm
1

 2  2  2 2 
2. v  0  v  2, v = +2 ...small intensity
 1   1 
2

 1  
1
2

Eovertone   2   e   2    e xe    e     e xe   2 1  3 xe  e cm
1

 2  2  2 2 
3. v  0  v  3, v = +3 ...negligible intensity
 1  1
2
 1 1
2

Ehot   3   e   3    e xe    e     e xe   3 1  4 xe  e cm .....etc.
1

 2  2  2 2 
Ignoring overtones and hot bands, we have  fundamental   excitation  E fundamental cm 1

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 Banwell P.120-121

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 Banwell P.120-121

Book: Banwell book

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 A Raman spectrometer typically contains four major components : an excitation
source, light collection system, monochromator, and a detector.

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