Raman Spectroscopy

Outline
• Introduction
• Theory of atomic vibrations and Raman
scattering
• Instrumentation for Raman spectroscopy
• Examples
 Chandrasekhara Venkata Raman

• 1888-1970
• Discovered the inelastic scattering
phenomenon in 1928
• Was awarded the Nobel Prize for
Physics in 1930
• Raman spectroscopy probes the vibration modes of materials,
much like infrared (IR) spectroscopy.
• However, whereas IR bands arise from a change in the
dipole moment, Raman bands arise from a change in the
polarizability.
• Unlike IR spectroscopy, which is based on absorption,
Raman spectroscopy is a light-scattering technique
• Unlike other scattering techniques, which assume that the
scattering event is elastic, Raman scattering is inelastic (the
scattered radiation has a frequency different from the incident
radiation).
• In many cases, transitions that are allowed in Raman are
forbidden in IR, so these techniques are often complementary.
 Applications of Raman Spectroscopy
Raman Spectroscopy is a method of determining modes of molecular
motions, especially vibrations. It is predominantly applicable to the qualitative
and quantitative analyses of covalently bonded molecules.

Extra:
-Identification of phases (mineral inclusions, composition of the gas phase inclusions)
-Anions in the fluid phase (OH-, HS-, etc.)
-Identification of crystalline polymorphs (Sillimanite, Kyanite, andalusite, etc.)

-Measurement of mid-range order of solids

-Measurement of stress

-High-pressure and High-temperature in situ studies

-Phase transition and order-disorder transitions in minerals (quartz, graphite)
-Water content of silicate glasses and minerals
-Speciation of water in glasses
 Energy Scheme for Photon Scattering

Virtual State
Energy

h0 h0+hm
h0 h0 h0 h0hm

E0+hm

E0
IR Rayleigh Stokes Anti-Stokes
Absorption Scattering Scattering Scattering
(elastic)
Raman
E-hvm
(inelastic)

,The Raman effect comprises a very small fraction

.about 1 in 107 of the incident photons
 IR Spectrography - Absorption

I0() I()

Laser Sample detector

Raman Spectrography - Scattering

Sample

 - Raman

Laser - Rayleigh detector

Infrared absorption and Raman scattering

0 50 100 150 200 250 300

-1
Frequency (cm )

-300 -200 -100 0 100 200 300

-1
Raman shift (cm )
 Raman Spectrum
A Raman spectrum is a plot of the intensity of Raman scattered radiation as a
function of its frequency difference from the incident radiation (usually in units of
wavenumbers, cm-1). This difference is called the Raman shift.

Raman Spectrum of CCl4

• Introduction
• Theory of atomic vibrations and Raman scattering
• Instrumentation for Raman spectroscopy
• Examples
The simplest real vibrating system:
a diatomic molecule
x1 K x2

m1 m2

m1m 2  d 2 x1 d 2 x 2  Just like

 2
 2    K x1  x 2 
m1  m 2  dt dt  Hooke’s
displacement law: F=kX
Reduced mass d 2q
 2  K  q
dt

 q  q 0 cos2 m  t 

1 K
:Where m 
2 
Scattering of radiation from a diatomic molecule
q  q 0 cos2 m  t 

E  E 0 cos20  t  ?

Induced dipole moment: P   E   E 0 cos20  t 

For a small amplitude of vibration, the   

   0     q  
polarizability  is a linear function of q:  q q  0

  
 P   0 E 0 cos20  t      q 0 cos2m  t   E 0 cos20  t  
 q q  0
1   
  0 E 0 cos20  t     q 0E 0 cos2 0   m  t   cos2 0   m  t 
2  q q  0

Rayleigh Stokes Anti-Stokes

scattering scattering scattering
 Example 1: the vibration modes of CO 2

Raman
Active

IR Active

IR Active

1   
P   0 E 0 cos20  t     q 0E 0 cos2 0   m  t   cos2 0   m  t 
2  q q 0
Example 2: the vibration modes of H2O

All the modes are both

Raman & IR Active
 Normal vibrations of CH2Cl2

 = stretching
 = bending
 Selection rules
0 and 1 are the wavefunctions of a ‘molecule’ before and after a
vibrational transition, respectively.

Ii    0 i 1 dV    0 x i 1 dV
i ( i = x,y,z ) are the components of the dipole moment.
If one of the integrals i  0, than the transition is IR active

Px   xx  xy  xz  E x 
 P     yy

 yz  E y 
 y   yx  
 Pz    zx  zy  zz   E z 

Iij    0 ij 1 dV    0 x i x j 1 dV
ij ( i,j = x,y,z ) are the components of the polarizability tensor.
If one of the integrals ij  0, than the transition is Raman active
 The simplest Raman active crystal:
1D chain with 2 atoms in the unit cell

m1 m2
K

u2n u2n+1

:Equations of motion m1u 2 n  K u 2 n 1  u 2 n 1  2u 2 n 

m 2u 2 n  K u 2 n  2  u 2 n  2u 2 n 1 

:Assume the solutions u 2 n  A1  exp i2t  2nka 

u 2 n 1  A 2  exp i2t  2n  1ka 

2 1 K K 2 4K 2 sin 2 ka 
:Obtain the frequencies   2   2
 
4    m1m 2 

 Outline

• Introduction
• Theory of atomic vibrations and Raman scattering
• Instrumentation for Raman spectroscopy
• Examples
A Typical Raman System
 Typical geometries for Raman scattring

90o scattering

180o scattering
 Spectrographs for Raman

Spex 1877 triple

monochromator

Spex 1403/4 double

monochromator
 Photo-Detectors

Charge coupled device (CCD)

Photodiode array detector

An example of Raman spectroscopy
A quick reminder of what CNTs look like:
The first major study of CNTs using Raman Spectroscopy
in: SCIENCE VOL. 275 10 JANUARY 1997
(4 years after CNTs were discovered by Iijima)
From the aforementioned article: These were the original “modes”
thought to have been in an SWNT.
Note the UNIT CELL in the upper right.
Of course, I made life easier for you all by not giving you the
“real” article which was 19 pages long
Three-dimensional
topographic image of a
SWNT grown

Explanation:
Variations in Raman
spectrum reflect
changes in the
molecular structure
caused by external
stress, catalyst particles,
or local defect, etc.
Change in Raman spectrum (2000 cm-1 – 500 cm -1) during extrusion
of EVA copolymer samples (2 % - 43.1 % wt VA)
Raman spectrum of P22
virus at a concentration
of 80 g/mL and a
sample volume of just 2
L. Incident
wavelength: 514.5 nm

Note the broad water

peak at 3000-3700 cm-1.
the peak at 2950
includes the aliphatic C-
H transitions of the
protein and DNA.

The peak at 2573 is the

-SH group of the Cys-
405 of the capsid
protein. It is visible
despite representing
just one of every 20,000
bonds in the virion.
C. Balachandran et al. / Cement and
Concrete Research 92 (2017) 66–74
The synthesized carbon were also characterized using Raman spectroscopy to
further establish the production of sp2 carbon materials. Fig. 3 shows that MCMs
produced using co-templating method has similar characteristic as carbon synthesis
using Pluronic F127 with the typical Raman peaks corresponded to sp2 carbon
occurred at 1595 cm1 and 1335 cm1. The G band at 1595 cm1 is corresponded to
an E2g mode of graphite layer meanwhile the D band at 1335 cm1 is associated
with the vibrations of disordered carbon presumably from carbon atoms with
dangling bonds of disordered graphite
M. Ulfa et al. / Science of the Total Environment 711 (2020) 135066
Teknik Informasi yang diperoleh
Difraksi Sinar-X Struktur kristal, Kristalinitas, Ukuran kristal,
(XRD) Jumlah/konsentrasi fasa, Dispersi
  permukaan
Spektroskopi Gugus fungsi
inframerah Jumlah gugus per gram
(FTIR) Kristalinitas
 
Spektroskopi Struktur molekul
UV-vis DR Ukuran partikel
FTIR probe Keasaman/basaan permukaan: jenis
molecule (Bronsted/Lewis), jumlah (mmol/g) dan
  kekuatan situs asam (kuat/lemah)
Solid state MAS Pergeseran kimia (jumlah)
NMR Struktur (tetrahedral/oktahedral)
Keasaman permukaan, Si/Al framework www.its.ac.id
Teknik Informasi yang diperoleh
Gas adsorption Luas permukaan
Ukuran dan volume pori
Jumlah mikro dan mesopori
Distribusi ukuran pori
Scanning Electron Morfologi permukaan
Microscopy (SEM- Ukuran partikel
EDX) Analisis unsur
Temperature Jumlah asam/basa
Programmed Kekuatan asam/basa
Desorption / Suhu reduksi/oksidasi
Reduction / Luas permukaan logam
Oxidation Dispersi logam
(TPD/R/O), Interaksi permukaan
chemisorption www.its.ac.id