Raman Spectra:
Discovered by [Link]
When a beam of monochromatic light is allowed to pass through
organic substances such as benzene ,toluene etc, the scattered
light contains additional frequencies which may be greater,lesser
or equal to than that of the incident [Link] effect is known as
Raman Effect.
Stokes lines,antistokes lines
Rayleigh ScatteringWhen the molecule collides with a photon,the
collisions maybe elastic or [Link] the collision is elastic,then the
total energy of the molecules and the photons remain the same.
Here the molecule will not get scattered without absorbing photon
[Link] collision will merely induce forced oscillations in the
[Link] will give rise to Rayleigh Scattering.
Stokes lines and Anti-Stokes lines:
If the collision between the molecule and photon is inelastic,then
there is a transfer of energy . Before collision the molecule is
present in the lower energy level of the ground state after collision
with the photon it reaches the higher level of the ground [Link]
frequency of the emitted photon is [Link] are Stokes lines.
Before collision the molecule is present in the higher energy level
of the ground state after collision with the photon it reaches the
lower energy level of the ground [Link] frequency of the
emitted photon is [Link] are Anti-Stokes lines.
If ν I --incident frequency ν s --Scattered frequency
Then Raman Shift Δ ν = ν I ― ν s
For Stokes lines Raman Shift Δ ν is positive. ν ˂ ν
s I
Raman lines at lower frequencies are called Stokes lines.
For Anti Stokes lines Raman Shift Δ ν is negative. ν ˃ ν
s I
Raman lines at higher frequencies are called Anti Stokes lines
For Rayleigh Scattering Raman Shift Δ ν is zero.
Characteristics of Stokes lines and Antistokes lines :
The intensity of Stokes lines is always greater than the
corresponding anti Stokes lines.
Raman frequencies are identified with Infra red vibrational
frequencies.
Raman Lines are symmetrically displaced about the parent line.
When the temperature rises,their individual separations from the
parent line decreases.
The frequency difference between the modified and parent line
represents the frequency of the absorption band of the material.
Differences between Stokes and Antistokes lines
Stokes lines Antistokes lines
1)Frequency of scattered 1)Frequency of scattered lines
lines is less than incident is more than incident light.
light.
2)Occurs by molecules at 2)Occurs by molecules at
lower energy level,which higher energy level,which
are more populated. are less populated.
3) These lines are more 3) These lines are less
intense with high intensity intense with low intensity of
of absorption. absorption.
4)At low temperature,these 4)At high
take place more frequently. temperature,molecules are
raised to higher energy state
and the lines gradually
increase.
INTENSITY DIFFERENCE
Scattering intensity is proportional to the square of induced dipole
[Link] a vibration does not greatly change the
polarizability,then the polarizability derivative will be near zero.
The intensity of the Raman band will be low.
INTENSITY
The intensity of spectral transitions is determined by :
a)Boltzmann Population:
–ΔE/KT
N/N0 =e
N= Number of molecules in the excited state
N0 = Number of molecules in the ground state.
ΔE = Difference in energy between the ground state and excited state.
K- Boltzmann constant
T =Temperature
If ΔE is large N/N0 would be small i.e. number of molecules in the
excited state would be less than the number of molecules in the ground
state.
Hence transitions ,originating from ground state to higher energy state are
more intense ,than transitions from first excited state to higher energy state.
b)Transition Probability: is the probability of transitions between two energy
levels.
The molecule on absorption of a photon does not go anywhere it pleases ,it
ends up in an energy level determined by the selection rule.
Transitions which obey selection rule are allowed transitions and those which
do not obey selection rule are forbidden transitions.
Allowed transitions are having greater intensity than forbidden transitions.
The intensity of Stokes lines are proportional to the number of atoms in the
ground [Link] intensity of anti-Stokes lines are proportional to the number
of atoms in the excited state.
Since the number of atoms in the ground state is more than the number of
atoms in the excited state the intensity of Stokes lines is more than the
intensity of anti Stokes lines.