EP405Jul2021 (IR Raman Slides)

3.
Spectroscopic methods
Typical questions asked : what are the suitable probes ?
What are the elements present in the sample?
The probe should be able to ''fingerprint'' the atoms
irrespective of the valence state they are in.
So the ''core levels'' should be identified (~100 ev – 1keV) Relatively high

High energy probes needed. These are typically energy probes.
XPS (X-ray photoelectron spectroscopy) also called : Periodicity of lattice
ESCA (Electron spectroscopy for Chemical Analysis) plays almost no role.
UPS (Ultra violet Photoelectron Spectroscopy)
What kind of bonds are there ?

Bonds are usually identified by their spring constants.
Usually Raman spectrum.
What is the electronic band structure? Band gaps?

Optical absorption, Photoluminescense, Angle resolved
Photo-emission (ARPES)
Relatively low
What is the phonon band structure? energy probes
Raman & Brillouin scattering
Thermal neutron scattering
Similar questions for molecules.....functional groups, excited states,

type of bond...
Scattering from molecules and solids
Molecules:
Raman scattering is a weak
process: 1 in 106 – 107 incident
photons
Most of the incident radiation will

be ''Rayleigh scattered'' (no
change in energy)
( )
2 2
8 π N α 1+cos θ
I =I 0 4 2
λ R
α : polarizability
Selection rule for HCl

(IR spectra)
vibrational levels
Δ ν = ±1 : why?
vibration & rotation ?
How stiff are the molecular springs (bonds)?
Suppose spectra of a diatomic molecule A-B is given
ω = μ √k
Calculate the reduced mass μ

−1
Then calculate k =480 Nm for HCl
So ∼0.5 kg will stretch this by 1 cm
5
(1 N =10 dyne)
Data: R.S Drago : Physical Methods for Chemists

Which energy levels do the transitions correspond to ?
Q branch : DJ=0
P branch : DJ=-1
R branch : DJ =+1
As the ''dumb-bell“ rotates,

the spring stretches out a
little changing the
rotational intertia
( )
E (ν , J ) = ℏ ω ν+
1
2
2 2 1
( )
+B e J (J +1) − D e J ( J +1) −α ν+ J ( J +1)
2
Uncoupled rotation & vibration Interaction between rotation & vibration
Rotation of the molecules (typically matches microwave energies)
Ĵ2 ⃗
P is the pre-existing
H = + ⃗p . E electric dipole moment
2I
2 J ( J +1)
EJ = ℏ
2I
⃗ | JM 〉
W = 〈 J ' M ' | ⃗p . E
selection rule (moment parallel to rotor axis)

Δ J =±1 Δ M =0 if M =0
Δ J =0,±1, Δ M =0 if M ≠0
Spherical rotor:
. E J +1 − E J ℏ All moments of inertia are
. .ν = = (J +1)
h 2π I equal.
The matrix elements are to be calculated between spherical Symmetric rotor :

harmonics. P is fixed, E is the electric field of incident Two moments are equal
radiation. Selection rules tell you which integrals will NOT
vanish. Linear rotor:
One moment is zero.
The typical values of the absorption are in the microwave to IR
Asymmetric rotor:
Note that the rotational intertia is a measure of the size of the All moments are unequal.
molecule.
A traditional example : IR spectra of HCl molecule
https://franklycaroline.com/writing/infrared-spectrometric-rotational-and-vibrational-analysis-of-hcl-and-dcl/
What changes if H is replaced with D ?
Notice the change in the x values, but the overall pattern is still same
https://franklycaroline.com/writing/infrared-spectrometric-rotational-and-vibrational-analysis-of-hcl-and-dcl/
IR spectra in gas liquid & solid phase would be different
WATER VAPOUR
IR spectra in gas liquid & solid phase would be different
Hydrogen bonding and hindered

rotations due to presence of other
molecules can change the
spectrum very significantly
Data ffrom : http://www1.lsbu.ac.uk/water/water_vibrational_spectrum.html

(A collection of lot of data about the spectrum of water and its molecular dynamics)
Vibrations of the H 2 O molecule : matches IR frequencies
http://www1.lsbu.ac.uk/water/water_vibrational_spectrum.html
What is the Terahertz gap ?
Vibration-Rotation spectra : the overall picture
Consider a AB type molecule.
Write the problem in terms of reduced mass and

relative distance.
Quantize this harmonic oscillator about equilibrium

''bond length''.
The eignestates are Hermite polynomials as usual.
The dipole moment may fluctuate as the bond stretches.

For symmetric diatomic molecules (N2,H2,O2) this
does not happen. That is why they are ''IR-inactive''.
Vibration +
Rotation
p.E type matrix element would give zero if p is fixed, between states
n and n+1 or n-1, due to the nature of the hermite polynomials.
But if p changes proportional to the change in normal co-ordinate

then the matrix element would be non-zero between n and n + 1.
So the first order derivative of the dipole moment w.r.t the

relevant normal co-ordinate must be non-zero
This is the selection rule.

Raman spectrum : identifying the vibrations
Where does
the 1330 line
in diamond
come from?
Which stretch
should give
higher freq?
C=C Why?
C-C
C-C or C-H
C-H
Data:
Renishaw
instruments
Classical normal mode problem for molecules:

N atoms → 3N normal co-ordinates : masses known, find eigenfrequencies
Subtract : 3 + 3 degrees of freedom for rotation + translation
2 +3 degrees of freedom for rotation + translation (linear molecule)
Enumerate degeneracies, symmetries
Simple Raman spectrum : identifying the characteristic lines
Molecules with similar/nearly similar sections give signatures at close wavenumbers.

From known spectral lines → identify functional groups/ bond stretches.
What are the selection rules of Raman lines?

Handwaving argument....
Two transitions are involved : So J should change by 0 or 2.
More rigorous analysis : See I.M. Millis, Molecular Physics, 7, 549 (1964)
Molecular Physics, 8, 363 (1963)
Raman spectrum : identifying the characteristic lines
Rotation spectra of
molecular hydrogen
Rotational Raman
spectrum of H-H
Graphene/
HOPG
Data:
A Ferrari
Solid State Comm.
143, 37 (2007)
Raman and Brillouin scattering : What is the difference?
Both involve emission/absorption of a phonon :

Raman : OPTIC branches :
so higher in energy (~ THz typically)
Brillouin : ACCOUSTIC branches :
so lower in energy (~Ghz typically)
Since the shifts are much smaller, scattering by

accoustic phonon gives energy shifts that require
Fabry-Perot type arrangement to analyse.
Raman shifts can usually be distinguished by

grating.
Phonon spectrum
of diamond:
Where does the
1332 cm-1 line
come from?
Diamond Graphene
Brillouin scattering setup is more complex than Raman....
Fairly simple, very little

sample preparation
required.
Even some protable

versions are avaialable now.
Raman Spectroscopy. R.L. McCreery
Requires the
resolution of a Fabry-
Perot interferometer,
since the energy shifts
are far smaller.
Serc.carleton.edu/NAGTW
orkshops/mineralogy/miner
al_physics/brillouin.html

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3.

So the ''core levels'' should be identified (~100 ev – 1keV) Relatively high

What kind of bonds are there ?

What is the electronic band structure? Band gaps?

Similar questions for molecules.....functional groups, excited states,

Most of the incident radiation will

Selection rule for HCl

Calculate the reduced mass μ

Data: R.S Drago : Physical Methods for Chemists

As the ''dumb-bell“ rotates,

selection rule (moment parallel to rotor axis)

The matrix elements are to be calculated between spherical Symmetric rotor :

Hydrogen bonding and hindered

Data ffrom : http://www1.lsbu.ac.uk/water/water_vibrational_spectrum.html

Write the problem in terms of reduced mass and

Quantize this harmonic oscillator about equilibrium

The eignestates are Hermite polynomials as usual.

The dipole moment may fluctuate as the bond stretches.

But if p changes proportional to the change in normal co-ordinate

So the first order derivative of the dipole moment w.r.t the

This is the selection rule.

Classical normal mode problem for molecules:

Molecules with similar/nearly similar sections give signatures at close wavenumbers.

What are the selection rules of Raman lines?

Both involve emission/absorption of a phonon :

Since the shifts are much smaller, scattering by

Raman shifts can usually be distinguished by

Fairly simple, very little

Even some protable

Raman Spectroscopy. R.L. McCreery

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