Raman Spectroscopy: B.Sc. (H) Chemistry

Raman Spectroscopy
Part II: Rotational Raman spectroscopy
B.Sc. (H) Chemistry
Dr Anil Kumar Singh

Department of Chemistry
Mahatma Gandhi Central University
1
Correction in last PPT, Raman Spectroscopy, Part-I, Slide No. 11, Molecular Polarizability
The corrected version is following,
We know the trigonometric expression,

1
sin A sin B = {cos 𝐴 − 𝐵 − cos(𝐴 + 𝐵)}
2
𝜇 = (𝛼0 + 𝛽 𝑠𝑖𝑛2𝜋𝜈𝑣𝑖𝑏 𝑡)𝐸0 𝑠𝑖𝑛 2𝜋𝜈𝑡
𝜇 = 𝛼0 𝐸0 𝑠𝑖𝑛 2𝜋𝜈𝑡 +𝛽 𝑠𝑖𝑛2𝜋𝜈𝑣𝑖𝑏 𝑡 · 𝐸0 𝑠𝑖𝑛 2𝜋𝜈𝑡
1
𝜇 = 𝛼0 𝐸0 𝑠𝑖𝑛 2𝜋𝜈𝑡 + 𝛽𝐸0 {cos 2𝜋(𝜈 − 𝜈𝑣𝑖𝑏 ) − cos 2𝜋(𝜈 + 𝜈𝑣𝑖𝑏 ) 𝑡}
2
1 1
𝜇 = 𝛼0 𝐸0 𝑠𝑖𝑛 2𝜋𝜈𝑡 + 𝛽𝐸0 {cos 2𝜋(𝜈 − 𝜈𝑣𝑖𝑏 ) − 𝛽𝐸0 cos 2𝜋(𝜈 + 𝜈𝑣𝑖𝑏 ) 𝑡}
2 2
Rayleigh Scattering Stokes line Antistokes line

Rotational Raman Spectra
Rotational energy level of linear molecules is
𝜀𝐽 = 𝐵𝐽 𝐽 + 1 − 𝐷𝐽2 (𝐽 + 1)2 cm-1 (𝐽= 0,1,2……)
Neglecting the centrifugal distribution constant, D, the expression will be:

𝜀𝐽 = 𝐵𝐽 𝐽 + 1 cm-1 (𝐽= 0,1,2……)
Selection Rule
In Microwave Spectroscopy: ∆𝐽 = ±1 (Already learnt in unit 2)
In Raman Spectroscopy: ∆𝐽 = 0, ±2
In Raman spectroscopy the rotational quantum number changes by two units rather than
one is connected with the symmetry of the polarizability ellipsoid.
3
• For a linear molecule, it is evident that during end-over-end rotation the ellipsoid
presents the same appearance to an observer twice in every complete rotation.
• Rotation about the bond axis produces no change in polarizability.
• Only end-over-end rotations give the spectra.
Direction of Electric field
1 2
Polarisation ellipsoid is smaller due to high polarization
3 4
For a pure rotational change, the transition,
ΔJ = -2, can be ignored, so the upper state quantum number must necessarily be
greater than that in the lower state.
ΔJ = 0, represents no change in the molecular energy and hence we obtain Rayleigh
scattering only.
For the transition, ΔJ = +2,
∆𝜀 = 𝜀𝐽′=𝐽+2 − 𝜀𝐽′′=𝐽
Putting the values of J in the equation,
= [B(J+2)(J+3)]-[BJ(J+1)]
= B(J2+3J+2J+6)-BJ2-BJ
= BJ2+5BJ+6B-BJ2-BJ
= 4BJ+6B
= B(4J+6) cm-1 5
Since ΔJ = +2, we may label these lines S branch lines and write,
∆𝜀𝑠 = B(4J+6) cm-1 ( J = 0,1,2….)
where, J is the rotational quantum number in the lower state.
If the molecule gains rotational energy from the photon during collision we have a
series of S branch lines to the low wavenumber side of the exciting line (Stokes' lines),
while if the molecule loses energy to the photon the S branch lines appear on the high
wavenumber side (anti-Stokes' lines). The wavenumbers of the corresponding spectral
lines are given by:
νത𝑆 = νത𝑒𝑥. ± Δɛ𝑆 = νത 𝑒𝑥. ± B(4J+6) cm−1
where the plus sign refers to anti-Stokes' lines, the minus to Stokes' lines, and νത𝑒𝑥. is the
wavenumber of the exciting radiation.
6
If, νത𝑆 = νത 𝑒𝑥. Rayleigh line
Rotational
Raman Spectra
When the value J = 0, in the
equation,
ҧ ± B(4J+6) cm−1
𝜈𝑆ҧ = 𝜈𝑒𝑥.
it is seen immediately that the
separation of the first line from
the exciting line is 6B cm-1, while
the separation between
successive lines is 4B cm-1.
Picture credit: Fundamentals of Molecular Spectroscopy,

4th Ed. By Colin N. Banwell and Elaine M. McCash Stokes’ line Antistokes’ line 7
Rotational Raman Spectra Points to remember
• For diatomic and light triatomic molecules the rotational Raman spectrum will normally
be resolved and we can immediately obtain a value of B, and hence the moment of
inertia and bond lengths for such molecules.
• Homonuclear diatomic molecules (for example O2, H2) give no infra-red or microwave
spectra since they possess no dipole moment, whereas they do give a rotational Raman
spectrum.
• If the molecule has a centre of symmetry (as, for example, H2, O2, CO2), then the effects
of nuclear spin will be observed in the Raman as in the infra-red.*
• Thus for O2 and CO2 (since the spin of oxygen is zero) every alternate rotational level is
absent;
• For example, in the case of O2, every level with even J values is missing, and thus every
transition labelled J = 0, 2, 4, . . . is also completely missing from the spectrum.
• In the case of H2, and other molecules composed of nuclei with non-zero spin, the
spectral lines show an alternation of intensity.
8
*(For detailed study about the influence of Nuclear spin on IR spectra, see page no. 79, : Fundamentals of Molecular Spectroscopy, 4th Ed. By Colin N. Banwell
and Elaine M. McCash)
Reference
Fundamentals of Molecular Spectroscopy, 4th Ed.
By Colin N. Banwell and Elaine M. McCash
Next: Vibrational Raman Spectra

9
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10

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Raman Spectroscopy

Part II: Rotational Raman spectroscopy

B.Sc. (H) Chemistry

Dr Anil Kumar Singh

We know the trigonometric expression,

Rayleigh Scattering Stokes line Antistokes line

Neglecting the centrifugal distribution constant, D, the expression will be:

Polarisation ellipsoid is smaller due to high polarization

where, J is the rotational quantum number in the lower state.

Picture credit: Fundamentals of Molecular Spectroscopy,

Next: Vibrational Raman Spectra

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