Raman and Rayleigh Scattering

1. When a beam of monochromatic light is passed through

the transparent liquid or gases known as the scatterer, a
small fraction of it is scattered due to the collision
between the molecules of the scatterer and the photons
of the light.

2. Two cases are noticed depending upon whether the

collision between the molecules and the photons are
elastic or inelastic.
•  
1. If the Collision is Elastic:
The total energy of the molecules and the photons will remain unchanged which
means that there is no exchange or transfer of energy. The collision will
merely induce forced oscillations in the molecule. This will result in unmodified
lines and this kind of scattering of monochromatic light is known as the Rayleigh
scattering. 
The scattered photons have the same energy (frequency, wavelength and
color) as the incident photons but different direction.
2. If the Collision is Inelastic: Raman scattering
If the collision between the molecule and the photon is inelastic in
nature then, there will be the exchange or transfer of energy
between the molecule and the photons. This case is further
studied by subdividing into two special cases that will lead to the
explanation of the formation of stokes and anti-stokes lines.
 
Raman scattering is based on inelastic scattering of the
monochromatic light, usually a LASER light in the UV region,
near the Infrared region, and near the UV range.

Rayleigh scattering  is the predominantly elastic scattering of light

or other electromagnetic radiation by particles much smaller than
the wavelength of the radiation.
Stokes Raman scattering
The molecule is in the lower vibrational and rotational level before
the collision and is present in any one of higher rotational-
vibrational states of the same level (as allowed by selection rules)
after Excitation and emission of a photon.

Thus, the molecule absorbs or gains energy equal to the

difference in the two energy levels involved.

Because the energy is supplied by a photon of the incident light,

the frequency of the emitted photon is less.
Anti Stokes Raman scattering
Before the collision, the molecule is present in one of the excited
vibrational and rotational energy states but after the emission of a
photon, it occupies one of the lower vibrational energy states of the
same level according to the selected role.

Since the molecule imparts some of its intrinsic energy to the

incident photon, thus the emitted photon has higher energy and /or
frequency than the incident photon
Stokes lines can be observed towards the lower frequencies
and

anti-Stokes can be seen towards the higher frequencies, later

they are mirrored at the center of the Raman spectrum.

Nevertheless, Stokes lines are more intense in comparison with

the anti-Stokes counterparts, because the vibrational ground
state is more populated than excited states .
 This frequency modulation is specific to
molecular vibration, it is possible to analyze
composition of material information by
anayzing spectrum of Raman scattered light.
The Raman effect is named after Indian scientist C. V.
Raman, who discovered it in 1928 with assistance from his
student K. S. Krishnan.

Raman was awarded the 1930 Nobel Prize in Physics, for

his discovery of Raman scattering.

The effect had been predicted theoretically by Adolf

Smekal in 1923.
Diagram of Raman instrumentation:  Incident laser light (yellow) is scattered at the light
surface. 

Most of the light is scattered at the same wavelength at the incident light.  Light that is
Raman shifted also is scattered in a random directions. 

A lens is used to collect the light, and a filter is used to block the wavelength of the
incident light. 

Longer wavelengths (Raman scattering) is transmitted to the monochromator and detection

system. 

The frequency shift of the scattered light will determine the chemical structure of the
sample material.
 
Diagram of Raman scattering:  Incident light (yellow) that loses or gains no energy
is scattered back at the same wavelength is called Rayleigh scattering. 

If some of the energy is transferred to the ground state, the scattered light is
scattered at a longer wavelength (red). 

Fluorescence is another effect that causes light to be re-emitted at longer

wavelengths. 

It often masks Raman scattering.