Introduction to Raman spectroscopy

Frdric Datchi

datchi@impmc.upmc.fr
IMPMC, CNRS, Universit Paris 6, 140 rue de Lourmel,
75015 Paris, France
Nanomat NP427

Spectrum of excitations in condensed-matter

quasielastic

phonon
valence
electron
excitations

IR

plasmon
core-electron
excitation

Compton
profile

Vibrational spectroscopies
Infrared
Raman
Brillouin

Linear effect / widely used

Hyper-Raman
Non-linear
Coherent anti-Stokes Raman
effects /
Impulsive stimulated Brillouin Less used
..
Inelastic X-ray/neutron scattering - Requires large
facilities (neutron or synchrotron sources)

What is vibrational spectroscopy useful for ?

Identification of molecular species and bonding
types
Information about:
The intra/intermolecular potential
Crystalline structure
Elasticity
Electronic structure (resonance effect)

Introduction to Raman spectroscopy

The Raman effect was discovered by the

Indian physicist C. V. Raman for which he was
awarded the Nobel Prize in Physics in 1930.
Raman spectroscopy is now a widely used
technique which enables to probe vibrational
modes (or phonons) of a material in the range
of optical frequencies (THz)
The Raman effect originates from the
interaction of a electromagnetic (EM) wave
with the vibrations of a material.

Molecular vibrations
A molecule with N atoms has 3N-6 vibrational
degrees of freedom (3N-5 for a linear molecule)

In the harmonic approximation, these degrees of

freedom can be represented by normal modes
of vibration: each vibrational state may then be
expressed as a combination of
these normal modes.

The total vibrational energy is the sum of

independent harmonic oscillators of energy:

Ek hk (nk 1 / 2)

H2O molecule
Symmetric stretching
1

3657 cm-1

Antisymmetric
stretching 3

3756 cm-1

Bending 2

1595 cm-1

Normal modes of a crystal

In a crystal with N atoms, the 3N

degrees of freedom gives rise to 3N
normal modes of vibrations, or
phonons. 3 are acoustic modes
(GHz) and 3N-3 are optic modes
(THz)
A phonon in the crystal can be
described by a plane wave of
wavevector q, a set of displacement
vectors un and a pulsation
=2=2c/

un

In 1D, 2 atoms/unit cell:

Normal modes of a crystal

Acoustic modes

un

Optic
branches

Acoustic
branches

Optic modes

q
TO

LO

q
First Brillouin zone

Light scattering
Incident light
(I0 ,0 )
Reflected light
(IR ,0 )

Transmitted light
(IT ,0 )

Scattered light
(IS ,S )
Rayleigh
(S = 0 )
Elastic scattering

IS~10-3 I0

Brillouin

(S = 0 )

Acoustic
vibrations
~ 30-300 GHz

IS~10-6-10-9 I0

Raman
Optic
vibrations
~ 3-30 THz

Classical description of the Raman effect

A. Origin of the Raman effect (1)

Classical description of the Raman effect

A. Origin of the Raman effect (2)

dQ

Classical description of the Raman effect

A. Origin of the Raman effect (3)

3 scattered radiations:

Rayleigh wave

Elastic: =0

Stokes wave

Anti-Stokes wave

Inelastic: =0v

Classical description of the Raman effect

B. Selection rules. Comparison with IR spectroscopy

Raman selection rule :

IR absorption selection rule:

Classical description of the Raman effect

B. Selection rules. Comparison with IR spectroscopy

Classical description of the Raman effect

B. Selection rules. Comparison with IR spectroscopy

Classical description of the Raman effect

B. Selection rules. Comparison with IR spectroscopy

Classical description of the Raman effect

B. Selection rules. Comparison with IR spectroscopy

Classical description of the Raman effect

C. Scattered Raman Intensity

Classical description of the Raman effect

D. Classical vs quantum theory
Classical theory does not explain:
Raman scattering from rotational vibrations, since it
does not assign discrete frequencies to rotational
transitions
The resonnance Raman effect when 0 is close to an
electronic absorption of the molecule
Surface enhanced Raman scaterring
.

Classical description of the Raman effect

D. Classical vs quantum theory
Stokes/anti-Stokes intensity ratio:
Classical theory: IS/IAS1 and does not depend on T
Quantum theory:

Where
This relation can be used to measure T

Raman effect in a crystal (classical theory)

Raman effect in a crystal (classical theory)

In addition to the elastic scattered wave, we thus again obtain two

scattered waves at different frequencies:
The Stokes wave with
The anti-Stokes wave with

and
and

Both frequency and wavevectors are conserved in the scattering process

Raman probes zone-center phonons

Since kAS/S=k0q, |q| 2 |k0 |=2 n.0 /c=2n/0 . For a visible laser,
~500 nm. Using n=3, |q| 4.105 cm-1.

|q |<< |Kmax,BZ|=2/a 108 cm-1 (a~5 )

q is very close to the Brillouin zone center (q0).

Defect-induced Raman modes

When the crystal is not perfect, such as in the presence of defects, the
translational symmetry is violated and so is the conservation rule of wavectors.
In this case, modes with q0 can become active

Raman spectrum of a high-purity

And defective graphite sample

LO-TO splitting (1)

When a vibrational mode is both Raman and infrared active, the electric field
produced by the vibrating permanent dipole couples with the longitudinal
vibrations but not the transverse ones. As a result, the frequency of
longitudinal optical (LO) wave, LO , is larger than the frequency of the
transverse optical (TO) wave, which is unperturbed: TO=q.
In the Raman spectrum, this translates in two peaks at different frequencies
for the same mode but different polarizations (L or T). The magnitude of this
splitting depends on the effective charge associated to the vibrational mode
and and dielectric permittivity. It will not always be large enough to be
resolved.

TO mode: E q E.q=0

LO mode: E // q E.q0 : The E field adds

a restoring force

LO-TO splitting (2)

In a cubic diatomic crystal (e.g. NaCl) it can be shown that the frequencies of
the LO and TO waves are related by:

0
=

where 0 and are respectively the static and infinite frequency dielectric
constants. This relation is known as the Lyddane-Sachs-Teller relation
A generalized form of the Lyddane-Sachs-Teller relation holding for any crystal
was proposed by Cochran and Cowley:
33

=1

0
=

Higher order Raman effect

So far we have only considered the first-order Raman effect, produced by the
scattering of a single phonon. The second-order Raman effect occurs when light is
scattered simultaneously by two phonons. The conservation of energy and
wavevectors impose:

S= 0 (q1 + q2)
kS = k0 (q1 +q2)
Since |kS|| k0|, q1 +q2 0: the vavevectors of the two phonons should be opposite,
but can have any value in the Brillouin zone. This produces a continuum spectrum, by
contrast with the line spectrum of the first-order Raman effect.

Diamond Raman spectrum

(0=228.9 nm)

Raman tensor and scattered intensity

Crystal symmetry and the Raman effect

If we neglect the slight difference in frequency of the incident and
scattered radiation, then the Raman tensor R is symmetric, like , ie:
Rxy=Ryx
The symmetry of the crystal and of the vibrational modes impose
constraints on the Raman tensor, such that only some of its
components will be non-zero.
The scattered radiation will thus vanish for certain choices of the
polarizations e0 and es . These defines additional selection rules for
Raman scattering in crystals which are useful for determining the
symmetry of Raman active phonons.
A general rule is that the Raman tensor of odd-parity phonons in
centrosymmetric crystals must vanish, whereas they are infrared
active.

Using symmetry to determine Raman or IR activity (1)

Example: NH3 molecule

Normal modes

A1

Point group C3v

Character table for C3v point group

C3
v

A1

2C3 (z)

3v

translations,
rotations

IR

Raman

A1

xx+ yy; zz

A2

-1

Rz

-1

(x, y) (Rx, Ry)

X,Y

(xx- yy, xy)

(yz- zx)

Using symmetry to determine

s Raman or IR activity (2)
Solid NH3 at high pressure: Phase IV, space group P212121 (D24)
Molecular symmetry

Site

Crystal

C3v

C1

D2 (P212121)

A1 (1 2 Tz)
A2 (Rz)
E( 31

The number of observed

modes constrains the
symmetry of the crystal

A
4

A
B1
B2
B3

TZ
TY
TX

R
R, IR
R, IR
R, IR

2T R )
xy xy

45 Raman active modes:

- 21 lattice modes : 6A + 5B1 + 5B2 + 5B3
- 24 internal modes : 4 1 + 4 2 + 8 3 + 8 4
33 IR active mode:
- 15 lattice modes : 5B1 + 5B2 + 5B3
- 18 internal modes : 3 1 + 3 2 + 6 3 + 6 4
3 acoustic modes: 1 B1+ 1B2 + 1B3

Polarized Raman scattering (single crystal)

Polarized Raman scattering uses the fact that Raman scattering from a
crystal depends on the direction of polarization of light: one is able to
select modes of a given symmetry using the proper scattering
geometry

e0 // c

Polarizer
(choose eS)
c

e0 // b
LASER

D2 Raman Tensor
D2

Rxx

Ryy

Rzz

Rxy

Rxz

Ryz

B1

Tz,Rz

B2

Ty,Ry

B3

Tx,Rx

This method is extremely powerful to assign vibrational modes of a crystal

Experimental aspects

Raman setup (backscattering)

LASER

LENS

Spectrometer
Entrance Pinhole

LENS

Beam Splitter

Scattered light

Sample

Triple stage spectrometer (T64000)

Czerny-Turner Config. .

Raman and fluorescence

UV Laser
Green Laser
Red Laser

What you will study during the practical

Two samples
1. Graphite and graphene

2. Quartz single crystal