Introduction to Basics of

Raman Spectroscopy

Chandrabhas Narayana
Chemistry and Physics of Materials
Jawaharlal Nehru Centre for Advanced Scientific
Research, Jakkur P.O., Bangalore 560064, India
cbhas@jncasr.ac.in
http://www.jncasr.ac.in/cbhas

Lecture at MASTANI Summer School, IISER, Pune, June 30, 2014 to July 12, 2014
July 11, 2014
What happens when light falls
on a material?
Transmission
Reflection
Absorption
Luminescence

Elastic Scattering
Inelastic Scattering
 Raman Spectroscopy
1 in 107 photons is scattered inelastically

virtual
state

Scattered
Rotational Raman

Excitation
Vibrational Raman
Electronic Raman

v” = 1

v” = 0
Infrared Raman
(absorption) (scattering)
Raman visible through unaided eye
Raman, Fluorescence and IR
Absorption
Scattering and emission Absorption
 Concept of normal modes in a
molecule
• There are 3N possible movements in a molecule made of N
atoms, each of which moving in one of three directions, x, y and
z.
– There are three transitional movements: all atoms in the
molecule moving in x, y or z direction at the same time.
– There are three rotational movements around x, y or z-axis
• Linear molecules are exceptions because two axes that
are perpendicular to the molecular axis are identical.
– The rest of movements are vibrational movements
• For linear molecules, 3N – 5 movements
• For non-linear molecules, 3N – 6 movements
– All vibrational movements of the sample can be described as
linear combinations of vibrational normal modes.
 Vibrations
Sym. Stretching
in Molecules
8086 cm-1 = 1 eV
HCl  = 2991 cm -1
HF  = 4139 cm-1

Asym. Stretching Sym. Bending

H2O 1 = 3835 cm-1 3 = 3939 cm-1 2 = 1648 cm-1

Asym. Bending
NH3 1 = 3505.7 cm-1 3 = 3573.1 cm-1 2 = 1022 cm-1 4 = 1689.7 cm-1

SF6 5 = 643.35 cm-1 2 = 615.02 cm-1 6 = 348.08 cm-1

1 = 774.55 cm-1 3 = 947.98 cm-1 4 = 523.56 cm-1

 Vibrational Spectroscopy
For a diatomic molecule (A-B), the bond between the two
atoms can be approximated by a spring that restores the
distance between A and B to its equilibrium value. The
bond can be assigned a force constant, k (in Nm-1; the
stronger the bond, the larger k) and the relationship
DAB between the frequency of the vibration, , is given by the
relationship:
k or, more typically k
  2 c  
 
where , c is the speed of light,  is the frequency in “wave
numbers” (cm-1) and  is the reduced mass (in amu) of A
and B given by the equation: m m
0 rAB   A B
m A m B
re
e = equilibrium distance between A and B

DAB = energy required to dissociate into A and B atoms

 Vibrational Spectroscopy
k
2 c   can be rearranged to solve for k (in N/m): k  5 . 8 9  1 0 5
2

Molecule  (cm-1) k (N/m)  (amu)
HF 3962 878 19/20
HCl 2886 477 35/36 or 37/38
HBr 2558 390 79/80 or 81/82
HI 2230 290 127/128
Cl2 557 320 17.5
Br2 321 246 39.5
CO 2143 1855 6.9
NO 1876 1548 7.5

N2 2331 2240 7
For a vibration to be active (observable) in an infrared (IR) spectrum, the
vibration must change the dipole moment of the molecule. (the vibrations for
Cl2, Br2, and N2 will not be observed in an IR experiment)
For a vibration to be active in a Raman spectrum, the vibration must change
the polarizability of the molecule.
Classical Picture of Raman
Induced Polarization Polarizability

Stokes Raman
Anti-Stokes Raman
Mutually exclusive principle
 Raman Scattering
Selection rule: v = ±1
Overtones: v = ±2, ±3, …


 z (t )   Emax cos 2 0t 
equil
zz

1 d zz 
rmax Emax cos 2 ( 0   vib )t 
2 dr
1 d zz 
rmax Emax cos 2 ( 0  vib )t
2 dr

Must also have a change in polarizability

Classical Description does not suggest any difference

between Stokes and Anti-Stokes intensities
h vib
N1 
e kT
N0
www.andor.com
Are you getting the concept?
Calculate the ratio of Anti-Stokes to Stokes scattering
intensity when T = 300 K and the vibrational frequency is
1440 cm-1.
h = 6.63 x 10 -34 Js
-34

k = 1.38 x 10-23 J/K

h vib
N1 
e kT ~ 0.5
N0
 Energy diagram and
Quantum picture
Virtual states

Raman cross section


<eg,p2|Her|p2,eb> <eb,p2|Hep|p1,ea> <ea,p1|Her|p1,eg>

photon |Es-Eb|x|Ei-Ea|
a,b

ex

g
Electronic states Vibrational states

If Ei = Ea or Es = Eb
We have Resonance Raman effect
 Intensity of Normal Raman Peaks
The intensity or power of a normal Raman peak
depends in a complex way upon
• the polarizability of the molecule,
• the intensity of the source, and
• the concentration of the active group.
• The power of Raman emission increases with
the fourth power of the frequency of the
source; - photodecomposition is a problem.
• Raman intensities are usually directly
proportional to the concentration of the active
species.
 Raman Depolarization Ratios

Polarization is a property of a beam of

radiation and describes the plane in
which the radiation vibrates. Raman
spectra are excited by plane-polarized
radiation. The scattered radiation is
found to be polarized to various degrees
depending upon the type of vibration
responsible for the scattering.
 Raman Depolarization Ratios

The depolarization ratio p is defined as

I
p 
I 

Experimentally, the depolarization ratio may be

obtained by inserting a polarizer between the
sample and the monochromator. The
depolarization ratio is dependent upon the
symmetry of the vibrations responsible for
scattering.
 Raman Depolarization Ratios

Polarized band: p = < 0.76 for totally

symmetric modes (A1g)
Depolarized band: p = 0.76 for B1g and B2g
nonsymmetrical vibrational modes
Anomalously polarized band: p = > 0.76
for A2g vibrational modes
Raman spectra of CCl4

Isotope effect
Cl has two isotopes 35Cl and 37Cl
Relative abundance is 3:1
 CCl4 Spectra

• 461.5 cm-1 is due to 35Cl4C

• 458.4 cm-1 is due to 35Cl337ClC
• 455.1 cm-1 is due to 35Cl237Cl2C
• What are the two question
marks?
• Why are these bands weak?
 Raman Spectra of Methanol and Ethanol
CH
stretching

20000

CCO
stretching
CH3 and CH2
Raman Intensity (arbitrary unit)

15000
deformation
OH
stretching
10000

CO
stretching
CH3
5000
deformation

500 1000 1500 2000 2500 3000 3500

Raman Shift (cm-1)

CASR
Significant identification of alcohols which differ just in one CH2-grou
 Peak position – Chemical identity –
CASR
Similar Structures
3,4-Methylenedioxymethamphetamine (MDMA) Methamphetamine
ecstasy
Raman Intensity (arbitrary unit)

500 1000 1500 2000 2500 3000 3500

Raman Shift (cm-1)
 The Mass Effect on Raman Spectra
Significant identification of salts (SO42-) which
differ just in the metal ion employed
1200

1000

800

Intensity (counts/s)
600

400
1000
200

800 Wavenumber (cm-1)

Intensity (counts/s)

600

400 Mg - SO4
200
Na2 - SO4
Wavenumber (cm-1)

CASR
CASR Peak positions – Chemical identity
Diasteromers
Ephedrine Pseudoephedrine
Raman Intensity (arbitrary unit)

500 1000 1500 2000 2500 3000 3500

Raman Shift (cm-1)
 Peak Position – Crystal Phases –
Polymorphs
Both Anatase and Rutile are TiO2 but of different
polymorphic forms - identical chemical composition,
different crystalline structures.
2 400

2 200

2 000

Rutile
1 800

1 600
In t e n s it y ( c n t )

1 400

1 200

1 000

800

600

400

200

200 400 600 800 1 000 1 200 1 400

Raman Shift (cm-1)

Anatase
CASR Peak Shift – Stress and Strain
Larnite ( – Ca2SiO4) inclusion in Diamond

Nasdala, L., Harris, J.W. & Hofmeister, W. (2007): Micro-spectroscopy of diamond. Asia Oceania
Geosciences Society, 4th Annual Meeting, Bangkok, Thailand, August, 2007.
Nasdala, L., Raman barometry of mineral inclusions in diamond crystals. Mitt. Österr. Miner. Ges. 149
(2004)
 CASR
Bandwidth – Crystallinity –
Structural order/disorder

Raman spectra of zircon, showing typical amorphous (blue)

and crystalline (red) spectra.
CASR Intensity – Concentration
4-Nitrophenol dissolved in CH2Cl2

3 500

1341.0
4-Nitrophenol in CH2Cl2_0,1 M
4-Nitrophenol in CH2Cl2_0,01 M
4-Nitrophenol in CH2Cl2_0,001 M
3 000

2 500
Intensity (cnt/sec)

2 000

1 500

1 000

500

0
1 200 1 400 1 600
Raman Shift (cm-1)
 Raman technique – what
CASR
requirements are needed?
Requirements for Raman technique to determine peak position, peak shift,
bandwidth and intensity

- Laser Excitation
- Reduction of stray light
- Collecting Optics
- Spectral resolution and spectral coverage
- Spatial resolution and confocality
- Sensitivity: subject to detector
- Light flux: subject to dispersion
 CASR What do we need to make a
Raman measurement ?
•Monochromatic Light source
Detector typically a laser

(A way of focusing the laser onto

the sample and then collecting the
Grating Raman scatter.)
•Sampling optics

•Rejection filter
(A way of removing the
scattered light that is not
Filter shifted( changed in colour).

Laser •Spectrometer and detector

Sample (often a single grating spectrometer
and CCD detector.)
 Demonstration of the very high
CASR spectral resolution obtained in the
triple additive mode
Rotation-Vibration Spectrum of O2

8000
Triple additive mode
Intensity (a.u.)

6000 Slit widths= 30 m

4000

2000 Triple subtractive mode . Slit=30 m

1520 1540 1560 1580

Wavenumber (cm-1)
CASR
Laser excitation – Laser Selection to
avoid fluorescence

Laser wavelength, 3 Raman shift, 3-1+

Laser
Laser wavelength, 3

Fluorescence

wavelength, 1 Raman shift, 1-1+

Laser wavelength: 3 < 2 < 1

 Laser excitation – Laser selection to
CASR
avoid fluorescence
60 000
Green spectrum: 532 nm laser
Red spectrum: 633 nm laser
50 000
Dark red spectrum: 785 nm laser
40 000
Intensity (cnt)

30 000

20 000

10 000 60 000

0 50 000
600 800 1 000
Wavelength (nm) 40 000
Intensity (cnt)

30 000

Fluorescence is wavelength dependent 20 000

Ordinary Raman is wavelength independent

10 000

0
1 000 2 000 3 000
Raman Shift (cm-1)
 CASR
Laser excitation – Laser selection to
avoid fluorescence
Commercial Hand Cream
x10 3

45

40

35

30
Intensity (cnt)

25

20

15

10

500 1 000 1 500 2 000 2 500 3 000 3 500

Raman Shift (cm-1 )

785 nm – 633 nm – 473 nm Reduction of Fluorescence

 Laser excitation – laser radiation
CASR
power

Laser wavelength: 473 nm Laser wavelength: 633 nm

Laser power at sample: 25.5 mW Laser power at sample: 12.6 mW
Objective N.A. Laser Radiation Objective N.A. Laser Radiatio
spot size power spot n power
(µm) (kW/cm2) size (kW/cm2)
(µm)

100× 0.90 0.64 ~7900 100× 0.90 0.85 ~2200

50× 0.75 0.77 ~5400 50× 0.75 1.03 ~1500
10× 0.25 2.31 ~600 10× 0.25 3.09 ~200
CASR Laser excitation – laser radiation
power
• Keep in mind: the usage of high numerical
objective lenses causes a very small spot
size of the laser which results in a high
power density
• To avoid sample burning radiation power
has to be adapted INDIVIDUALY to the
sample
CASR Collecting Optics
Collection solid angle
Large for high N.A. lens

Working distance
Small for low N.A. lens High N.A. lens
Low N.A. lens
Sampling volume
Working distance

Small for high N.A. lens θ

θ Large for low N.A. lens

Laser spot size

Small for high N.A. lens
Large for low N.A. lens

NA = n · sin ()

n: refraction index
: aperture angle
 Collecting Optics – Overview on
CASR
common objectives

Working distance
Objective N.A.
[mm]

x100 0.90 0.21

x50 0.75 0.38

x10 0.25 10.6

x100 LWD 0.80 3.4

x50 LWD 0.50 10.6

 Collecting Optics – what objective
CASR
should be used?
A distinction between opaque and transparent samples has to be made
For opaque samples, high N.A. lens works better because there is almost no
penetration of the laser into the sample. High N.A. lens enables

- High laser power density (mW/m3)  increases sensitivity

- Wide collection solid angle  increases sensitivity

Example for an opaque sample: 30 000 100 %

Silicon
Silicon wafer x100 – NA = 0.9 – 31.350 C/s
25 000
x50 – NA = 0.75 - 21.995 C/s
-20 70 % x10 – NA = 0.25 - 1.462 C/s
Intens ity (c nt/s ec )

20 000

15 000
Y (µm)

0
10 000

5 000
20 10 µm 5%
0

0
460 480 500 520 540 560 580 600 620
X (µm) Ram an Shif t (cm-1)
 Collecting Optics – what objective
CASR
should be used?
A distinction between opaque and transparent samples has to be made
For transparent samples, low N.A. lens works better because of penetration of
the laser into the sample. Low N.A. lens enables

- Large sampling volume  increases sensitivity

x10 3
cyclo_100xLWD
Sample: Cyclohexane cyclo_macro
14
Instrument: ARAMIS
100 %
Red: x100LWD, 7,000 cts/s
12
Blue: Macro lens, 14,500 cts/s
10
Intensity (cnt)

6
48 %

0
740 760 780 800 820 840 860 880
Raman Shift (cm-1 )
CASR
Spectral resolution and spectral
coverage
Schematic diagram of a Czerny-Turner spectrograph
Slit Collimating
mirror

Grating

Focusing mirror
Detector

Focal Length
 Spectral resolution and spectral
CASR
coverage
• Spectral resolution is a function of 1. dispersion, 2. widths of entrance slit
and 3. pixel size of the CCD

• Dispersion is the relation between refraction of light according to the

wavelength of light

• Dispersion is a function of the 1. focal length of spectrograph the 2.

groove density of the grating and 3. the excitation wavelength

• In general, long focal length and high groove density grating offer
high spectral resolution.
 Dispersion as a function of the focal
CASR
length

CCD Detector
Short focal length

Same grating
Same excitation wavelength

CCD Detector
Long focal length
CASR
Dispersion as a function of the focal
length vis-a vis wavelength
Dispersion in cm-1 / pixel
1800 gr/mm Grating
LabRAM (F = 300 mm)
LabRAM HR (F = 800 mm)
 Dispersion as a function of excitation
CASR
wavelength
-1
Horizontal lines indicate a relative Raman Shift of 3800 cm

244 - 269 nm (25 nm)

325 - 371 nm (46 nm)
457 - 553 nm (96 nm)
488 - 599 nm (111 nm)
514 - 639 nm (125 nm)
532 - 667 nm (135 nm)
633 - 833 nm (200 nm)
785 - 1119 nm (334 nm)
830 - 1210 nm (380 nm)
1064 - 1768 nm (704 nm)

200 400 600 800 1000 1200 1400 1600 1800

Wavelength [nm]
Same focal length
Same grating
CCD Detector

CCD Detector
Short wavelength Long wavelength
CASR
Spectral coverage - dependence from
excitation wavelength
Length of CCD Chip

x10 3
22
473 nm – 633 nm – 785 nm
20

18
Length of CCD Chip Same focal length
16 Same grating
Intensity (cnt/sec)

14

12

10
Length of CCD Chip
Relative Raman shift of 3100 cm -1
8 corresponds to 81 nm

4 Relative Raman shift of 3100 cm-1

corresponds to 154 nm Relative Raman shift of 3100 cm-1
2
corresponds to 252 nm
0
500 600 700 800 900 1 000
Wavelength (nm)
CASR Dispersion as a function of groove density

CCD Detector

CCD Detector
Low density groove grating
High density groove grating
Same focal length
Same excitation wavelength
 Spectral resolution as a function slit
CASR
width
Slit Slit Slit

One of parameters that determines the spectral resolution is the entrance

slit width. The narrower the slit, the narrower the FWHM (full width at half
maximum), and higher the spectral resolution.

When recording a line whose natural width is smaller than the

monochromator’s resolution, the measured width will reflect the
spectrograph’s resolution.
 Spectral resolution as a function of pixel
CASR
size
• Because a CCD detector
is made of very small

Detector
pixels, each pixel serves
as an exit slit (pixel size =
exit slit width)
• For the same size CCDs,

Detector
the CCD with a larger
number of smaller pixels
produces a larger number
of spectral points closer to
each other increasing the
limiting spectral resolution
Intensity

and the sampling

frequency
• 26 m pixel vs. 52 m
600 650 700
pixel (simulation)
Raman Shift (cm-1)
 CASR Choice of Laser for Raman

The choice of laser will influence

100
different parameters:
Silicium
• Signal Intensity: (1/4 rule applies to 10

Penetration depth (µm)

Raman intensity.
• Probing volume: spot size and 1

material penetration depth.

0,1
• Fluorescence: may overflow Raman
signal.
0,01

• Enhancement: some bounds only

react strongly at a certain wavelength. 0,001
200 300 400 500 600 700 800 900
Wavelength (nm)
• Coverage range and Resolution:
grating dispersion varies along the
spectral range.
 CASR Spatial resolution: penetration depth
Penetration depth in Silicon
244 nm 325 nm
0
2
4
6 Wavelength [nm]
244 nm 325 nm 457 nm 488 nm 514 nm 633 nm
8

D e p t h p e n e t r a t io n [n m ]
0

10
500
12

1000

1500

2000

2500

3000

 General: The larger the excitation wavelength, the

deeper the penetration.
 The exact values depend on material.
 CASR Spatial resolution: penetration depth

325 nm 488 nm 785 nm

Strained Si
of top layer

325 nm ~nm Strained silicon layer

Intensity a[ .u.]

Si of SiGe ~nm Uniform layer of SiGe

layer

~µm
488 nm Gradient SiGe layer
Si of silicon
substrate

Pure Si substrate
400 450 500 550
785 nm
Raman shift (cm-1)

 The higher the excitation wavelength, the deeper the penetration.

 CASR Spatial resolution: penetration depth
EXAMPLE
325nm laser results

The strain is not homogenous.

A characteristic, cross-hatch pattern is observed.
 CASR Spatial resolution and spot size
Laser spot size D is defined by the Rayleigh criterion:
excitation wavelength ()

D = 1.22  / NA

objective numerical aperture (NA)

With NA=n sinα

Spatial resolution is half of the laser spot diameter

CASR Confocality and Spatial Resolution
Nearly closed
confocal apertur

Sample

P P P P' P'

P'

Image P ' of laser focus P matches

exactly the confocal hole.

Length of
Laser Focus
Axial resolution of a Confocal Raman Microprobe

CASR
 Confocality and spatial Resolution
Narrow Hole:
Laser focus Collecting Raman radiation that
Wide Hole waist diameter originates only from within a
diffraction limited laser focal
Depth of volume with a dimension of:
laser focus
Focus waist diameter ~ 1.22  / NA
Sampling (d.o.f)
Depth of laser focus ~ 4  / (NA)2
Volume
Narrow Hole

Confocal z-scan against silicon

with different hole apertures
exc = 633 nm

CASR
Example of application using the confocality
principle : depth profile on a multilayer polymer
sample 5000
x
4000

Polyethylene

Intensity (a.u.)
3000

nylon 75 m 2000

Polyethylene 1000

z 0

1000 1200 1400 1600

Wavenumber (cm-1)

3000

2500

Intensity (a.u.)
2000

1500

1000

500

1000 1200 1400 1600

CASR Wavenumber (cm-1)

Thank you for your attention!
 Symmetry – Identity (E)
Identity operation (E)
This is a very important symmetry operation which is
where the molecule is rotated by 360º. In otherwords a
full rotation or doing nothing at all.
This appears in all molecules!!!
 Symmetry – Rotation (Cn)
Rotations (Cn)
These are rotations about the axes of symmetry. n
denotes 360º divided by the number for the rotation.

C2 = 180º C3 = 120º C4 = 90º C5 = 72º C6 = 60º

 Symmetry – Reflections ()
Reflections (h, d and v) These are reflections in a
symmetry planes (x, y and z).

h - Horizontal v - Vertical d - Diagonal

Plane  (y) Plane  (z) (dihedral) Plane (x)
perpendicular parallel the Diagonal Plane
to the highest to the highest that bisects two
rotation axis rotation axis axes
 Symmetry – Inversion (i)
Inversion centre (i)
These are where the molecule can be inverted through the
centre of the molecule (atom or space).
Symmetry – Improper Rotation (Sn)
Improper rotations (Sn)
These are rotations about the axes of symmetry
followed by reflections.
 Vibrational Spectroscopy
For polyatomic molecules, the situation is more complicated because there are more
possible types of motion. Each set of possible atomic motions is known as a mode.
There are a total of 3N possible motions for a molecule containing N atoms because
each atom can move in one of the three orthogonal directions (i.e. in the x, y, or z
direction).

A mode in which all the atoms are moving in the same

direction is called a translational mode because it is
equivalent to moving the molecule - there are three
translational modes for any molecule.

A mode in which the atoms move to rotate (change the

orientation) the molecule called a rotational mode - there
are three rotational modes for any non-linear molecule
and only two for linear molecules.

Translation Rotational
al modes modes
The other 3N-6 modes (or 3N-5 modes for a linear molecule) for a molecule
correspond to vibrations that we might be able to observe experimentally. We must
use symmetry to figure out what how many signals we expect to see and what atomic
motions contribute to the particular vibrational modes.
 Vibrational Spectroscopy and Symmetry

We must use character tables to determine how many signals we will see
in a vibrational spectrum (IR or Raman) of a molecule. This process is
done a few easy steps that are similar to those used to determine the
bonding in molecules.

1. Determine the point group of the molecule.

2. Determine the Reducible Representation, tot, for all possible motions of

the atoms in the molecule.

3. Identify the Irreducible Representation that provides the Reducible

Representation.

4. Identify the representations corresponding to translation (3) and rotation

(2 if linear, 3 otherwise) of the molecule. Those that are left correspond
to the vibrational modes of the molecule.

5. Determine which of the vibrational modes will be visible in an IR or

Raman experiment.
Finding the Point Group
 Vibrational Spectroscopy and Symmetry
Example, the vibrational modes in water.
The point group is C2v so we must use the appropriate character table
for the reducible representation of all possible atomic motions, tot. To
determine tot we have to determine how each symmetry operation
affects the displacement of each atom the molecule – this is done by
placing vectors parallel to the x, y and z axes on each atom and
applying the symmetry operations. As with the bonds in the previous
examples, if an atom changes position, each of its vectors is given a
value of 0; if an atom stays in the same place, we have to determine
the effect of the symmetry operation of the signs of all three vectors.

The sum for the vectors on all atoms is placed into the reducible
representation.
Make a drawing of the molecule and add in vectors
O on each of the atoms. Make the vectors point in
the same direction as the x (shown in blue), the y
H H (shown in black) and the z (shown in red) axes.
We will treat all vectors at the same time when we
are analyzing for molecular motions.
H O H
top view
 Vibrational Spectroscopy and Symmetry
Example, the vibrational modes in water. z y
The E operation leaves everything where it is so all nine O
vectors stay in the same place and the character is 9. H H x

The C2 operation moves both H atoms so we can ignore the

vectors on those atoms, but we have to look at the vectors on H O H
the oxygen atom, because it is still in the same place. The C2
vector in the z direction does not change (+1) but the vectors
in the x, and y directions are reversed (-1 and -1) so the H O H
character for C2 is -1.
The v (xz) operation leaves each atom where it was so we H O H
have to look at the vectors on each atom. The vectors in the v (xz)
z and x directions do not move (+3 and +3) but the vectors in
the y direction are reversed (-3) so the character is 3. H O H
The ’v (yz) operation moves both H atoms so we can ignore
the vectors on those atoms, but we have to look at the vectors
on the oxygen atom, because it is still in the same place. The H O H
vectors in the z and y directions do not move (+1 and +1) but ’v (yz)
the vectors in the x direction is reversed (-1) so the character
is 1. C E C  (xz) ’ (yz)
2V 2 v v
H O H
tot 9 -1 3 1
 Vibrational Spectroscopy and Symmetry
C2V E C2 v (xz) ’v (yz)
tot 9 -1 3 1

C2V E C2 v (xz) ’v (yz)

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
From the tot and the character table, we can figure out the number and types of modes
using the same equation that we used for bonding:
1
nX 
o rd e r
  # o f o p e r a t io n s in c la s s   ( c h a r a c t e r o f R R )  c h a r a c t e r o f X 
This gives:
1 1
n A 1

4

 1  9  1    1   1  1    1  3  1    1  1  1   nB1 
4

 1  9  1    1   1   1    1  3  1    1  1   1  
1
n A 2

1
4

 
1  9  1    1   1  1    1  3   1    1  1   1  n B 2 
4
1  9  1    1   1   1    1  3   1    1  1  1  
Which gives: 3 A1’s, 1 A2, 3 B1’s and 2 B2’s or a total of 9 modes, which is what we
needed to find because water has three atoms so 3N = 3(3) =9.
 Vibrational Spectroscopy and Symmetry

Now that we have found that the irreducible representation for tot is (3A1 + A2 + 3B1+
2B2), the next step is to identify the translational and rotational modes - this can be
done by reading them off the character table! The three translational modes have
the symmetry of the functions x, y, and z (B1, B2, A1) and the three rotational modes
have the symmetry of the functions Rx, Ry and Rz (B2, B1, A2).

C2V E C2 v (xz) ’v (yz)

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz

The other three modes (3(3)-6 = 3) that are left over for
water (2A1 + B1) are the vibrational modes that we might be
Translation Rotational able to observe experimentally. Next we have to figure out if
al modes modes we should expect to see these modes in an IR or Raman
vibrational spectrum.
 Vibrational Spectroscopy and Symmetry
Remember that for a vibration to be observable in an IR
spectrum, the vibration must change the dipole moment of the
molecule. In the character table, representations that change the
dipole of the molecule are those that have the same symmetry
as translations. Since the irreducible representation of the
vibrational modes is (2A1 + B1) all three vibrations for water will
be IR active (in red) and we expect to see three signals in the
spectrum.
For a vibration to be active in a Raman spectrum, the vibration
must change the polarizability of the molecule. In the character
table, representations that change the polarizability of the
molecule are those that have the same symmetry as the second
The three vibrational order functions (with squared and multiplied variables). Thus all
modes for water. Each three modes will also be Raman active (in blue) and we will see
mode is listed with a 
(Greek letter ‘nu’) and a
three signals in the Raman spectrum.
subscript and the C2V E C2 v (xz) ’v (yz)
energy of the vibration is
given in parentheses. 1 A1 1 1 1 1 z x2,y2,z2
is called the “symmetric
stretch”, 3 is called the A2 1 1 -1 -1 Rz xy
“anti-symmetric stretch” B1 1 -1 1 -1 x, Ry xz
and 2 is called the
“symmetric bend”. B2 1 -1 -1 1 y, Rx yz
The Geometry of the Sulfur Dioxide
Molecule
 Cs structure: 3 normal modes, all
having A' symmetry

The Cs structure should have 3 IR active fundamental

transitions. These three fundamental transitions also should
be Raman active. We would expect to observe three strong
peaks in the IR and three strong peaks in the Raman at the
same frequency as in the IR. All of the Raman lines would be
polarized because they are totally symmetric (A' symmetry).
 C2v structure: 3 normal modes, two
with A1 symmetry, one with B2  

The C2v structure should have 3 IR active fundamental

transitions. These three fundamental transitions also should
be Raman active.We would expect to observe three strong
peaks in the IR and three strong peaks in the Raman at the
same frequency as in the IR.
Two of the Raman lines are totally symmetric (A1 symmetry)
and would be polarized. One Raman line would be
depolarized.
The Dooh structure should have two IR active
fundamental transitions. It will have one Raman
active fundamental transition at a different
frequency than either of the IR peaks.. The
Raman line will be polarized.
 Experimental Observation
The experimental infrared and Raman bands of liquid
and gaseous sulfur dioxide have been reported in a
book by Herzberg 7 . Only the strong bands
corresponding to fundamental transitions are shown
below. The polarized Raman bands are in red.

Fundamental 2 1 3
IR (cm-1) 519 1151 1336
Raman (cm-1) 524 1151 1336
 Conclusion
The existence of three experimental bands in the IR
and Raman corresponding to fundamental transitions
weighs strongly against the symmetrical linear (Dooh)
structure. We usually do not expect more strong bands
to exist than are predicted by symmetry.
Group theory predicts that both bent structures would
have three fundamental transitions that are active in
both the IR and Raman. However all three of the
Raman lines would be polarized if the structure were
unsymmetrical (Cs symmetry). The fact that one
Raman line is depolarized indicates that the structure
must be bent and symmetrical (C2v symmetry).

The sulfur dioxide molecule has C2v symmetry.

Problems with Raman:
a)Very Weak – for every 106 photons only 1
photon Raman
a)Resonant Raman not feasible with every sample.
b)Absorption a better process than scattering
International and National Patent (2007), G.V. Pavan Kumar et al Current Science (2007) 93, 778.

Micro–Raman
Raman setup
Spectrometers
Optical fiber
Mono-
chromator
CCD
Focusing lens
Edge filter
Camera

Computer

Dichroic LASER
Mirror

Objective lens

Stage