Raman Spectroscopy

Raman effect is a 2-photon scattering process

These processes are inelastic scattering:
Stokes scattering: energy lost by photon:
- - (( - - ))
Photon in Photon out
No vibration Vibration
Anti-Stokes scattering: energy gained by photon:
(( - - )) - -
Photon in Photon out
Vibration No vibration

But dominant process is elastic scattering:
Rayleigh scattering
- - - -
Photon in Photon out
No vibration No vibration
If incident photon energy E; vibration energy v, then
in terms of energy, photon out has energy:
E-v Stokes scattering
E+v anti-Stokes scattering
E Rayleigh scattering




Representation in terms of energy levels:









Arrow up = laser photon in; Arrow down = Raman scattering out
Explanation of Raman effect: click under scattering
http://gepasi.dbs.aber.ac.uk/roy/ftir/emspec.htm

Here is another explanation, and a Raman
spectrometer
http://www-
personal.umich.edu/~jshaver/virtual/labeled/desc.html
Or
http://www-
personal.umich.edu:80/~jshaver/virtual/explain.html



Typical Raman spectrum
Plot of signal intensity vs Raman shift
(Raman shift, in cm
-1
= energy of photon in-energy of photon out)
-400 -300 -200 -100 0 100 200 300 400
0
10
R
e
l
a
t
i
v
e

i
n
t
e
n
s
i
t
y
Raman shift (cm
-1
)
Stokes
Rayleigh
anti-Stokes
-
2
7
7
-
1
1
2
2
2
6
2
7
9
1
1
4
Cs
2
NaBiCl
6
-Raman
shows 3
vibrations of
octahedral
BiCl
6
3-

Selection rule for Raman spectrum
Vibration is active if it has a change in
polarizability, o.
Polarizability is the ease of distortion of a bond. For
Raman-active vibrations, the incident radiation does
not cause a change in the dipole moment of the
molecule, but instead a change in polarizability.
In starting the vibration going, the electric field of
the radiation at time t, E, induces a separation of
charge (i.e. between the nuclear protons and the
bonding electrons). This is called the induced
dipole moment, P. (Dont confuse it with the
molecules dipole moment, or change in dipole
moment, because this is often zero).
P = oE
Example: There are 4 normal modes of CO
2
. Only v
1

is Raman active

is dipole moment;
o is polarizability;
Q is vibration coordinate, The slopes
are measured at Q = 0 (I.e. at the equilibrium position).


Change in
dipole
moment, ,
and
polarizability,
o, during CO
2

vibrations
v
1
v
3
Uses of Raman Spectroscopy
Raman spectroscopy has become more widely used
since the advent of FT-Raman systems and remote
optical fibre sampling. Previous difficulties with
laser safety, stability and precision have largely
been overcome.
Basically, Raman spectroscopy is complementary
to IR spectroscopy, but the sampling is more
convenient, since glass containers may be used
and solids do not have to be mulled or pressed into
discs.
Applications of Raman spectroscopy
Qualitative tool for identifying molecules from their
vibrations, especially in conjunction with infrared
spectrometry.
Quantitative Raman measurements
a) not sensitive since Raman scattering is weak. But
resonance Raman spectra offer higher sensitivity,
e.g. fabric dyes studied at 30-50 ppb.
b) beset by difficulties in measuring relative
intensities of bands from different samples, due to
sample alignment, collection efficiency, laser power.
Overcome by using internal standard.

Raman and fluorescence spectra
The diagram shows some of the energy levels of the uranyl ion. UO
2
2+


20000 cm
-1

| Energy

___________ 800 cm
-1
___________ 0 cm
-1

The vibrational level at 800 cm
-1
is the totally symmetric stretch.
The electronic levels are fairly continuous above 20000 cm
-1
.
What happens if you excite with a laser at (a) 15000 cm
-1
? (b)
21000 cm
-1
? (c) 22000 cm
-1
?
Raman vs IR spectroscopy
RAMAN IR
Sample preparation usually simpler
Liquid/ Solid samples must be free
from dust
Biological materials usually fluoresce,
masking scattering
Spectral measurements on vibrations Halide optics must be used-
made in the visible region-glass cells expensive, easily broken,
may be used water soluble
Depolarization studies are easily made IR spectrometers not usually
(laser radiation almost totally linearly equipped with polarizers
polarized)


More about polarizability
o, polarizability of molecule, related to mobility of
electrons (under applied radiation field in our present
case).
For atoms, same distortion is obtained for field in any
direction. Polarizability is Isotropic
For many molecules, polarizability depends on
direction of applied field, e.g. HH easier to distort
along bond than bond. Polarizability is anisotropic

Variation of o with direction is described by
polarizability tensor.



Calculation of Stokes and anti-Stokes intensity ratio
The Raman spectrum was
taken at 300 K using 1064
nm Nd-YAG radiation.
Check the intensity ratio
of the v
1
features at
278.5 cm
-1.

What can you say about
the intensity ratio of the
band at 112 cm
-1
?
Instrumentation

Dispersive Raman instruments
Laser Sample Double or triple monochromator
+
signal processing and output Photomultiplier tube

The monochromators are required to separate the weak
Raman signal from the intense, nearby Rayleigh
scattering. Typical lasers are Ar
+
(e.g. green line, 514.5
nm) or Kr
+
(e.g. yellow line, 530.9 nm).

New Raman systems

http://www.s-and-i.de/

Fourier transform Raman spectrometer
The Raman instrument can be on the same bench
as the FTIR. Often, a YAG:Nd
3+
laser (1064 nm) is
used to excite the sample, so that the excitation
energy is lower than the absorption band
energies of organic systems. Fluorescence is
then minimized.
Instruments may be combined with a microscope,
or optical fibre, so that scanning over a few
(microns)
2
of surface area, and Raman mapping is
easily performed.
Sampling techniques for Raman spectroscopy
If the sample is colourless, it does not absorb a visible laser
Raman spectroscopy is applicable to solids, liquids or
gases.
Gases:
use gas cell


Liquids and solids can be
sealed in a glass capillary:

If the compound is colored, it can absorb the laser,
get hot and decompose. Some techniques are:
Reduce the laser power (defocus) and/or change
wavelength;
Dilute the sample into a KBr pellet;
Cool the sample
Rotate or oscillate the laser beam on the sample


Number of bands in a Raman spectrum
As for an IR spectrum, the number of bands in the
Raman spectrum for an N-atom non-linear molecule is
seldom 3N-6, because:
polarizability change is zero or small for some
vibrations;
bands overlap;
combination or overtone bands are present;
Fermi resonances occur;
some vibrations are highly degenerate; etc
High resolution Raman spectra can show splittings
due to isotopic mass effects, for example: the v
1

Raman band of CCl
4
(corresponding tp the totally
symmetric stretching vibration) is split into 5
components.

461.5 cm
-1
is due to
35
Cl
4
C
458.4 cm
-1
is due to
35
Cl
3
37
ClC
455.1 cm
-1
is due to
35
Cl
2
37
Cl
2
C
What are the two question
marks?
Why are these bands weak?

Depolarization ratio of a vibrational mode in the Raman
spectrum
may give information about the symmetry of a vibration.

p
= depolarization ratio for polarized light = I
y
/I
z
= I

/I
||
This is different from the depolarization ratio for unpolarized light, see Infrared and Raman
SpectraPart A., K. Nakamoto 5th Ed. Wiley 1997. Pp. 97-101.
0s
p
<0.75; Raman line is polarized (p). Vibration is totally symmetric

p
= 0.75. Raman line is depolarized (dp). Vibration is not totally
symmetric.

CCl
4
Special types of Raman spectroscopy
(see Hollas, Modern Spectroscopy, Wiley)
Resonance Raman (RR) scattering
When the laser excitation frequency is near (or coincident) with an
electronic absorption band, intensity enhancement can occur by a
factor of 10
2
-10
6
, compared with normal Raman scattering.
Electronic transitions are often localized in one part of a molecule,
so that RR provides information about vibrations of the
chromophore, especially those exhibiting a large change in
geometry between the two electronic states.
RR is used in analytical chemistry to achieve detection limits 10
-6
-
10
-8
M.
Surface enhanced Raman spectroscopy (SERS):
Raman scattering is enhanced (typically by 10
3
-10
6
times) when the
analyte is adsorbed on colloidal metallic surfaces,
e.g. on colloidal Ag prepared by reduction of Ag
+
with citrate, in
particle size range 25-500 nm.


Stimulated Raman scattering (SRS)
The Raman scattering from a laser is observed in the forward
direction from the sample (i.e. in the same direction, or at a small
angle to the incident laser radiation).
Vibrational progressions are observed for certain modes.
Coherent anti-Stokes Raman spectroscopy (CARS)
Radiation from two lasers is incident on the sample, and the
intensity of the outgoing wave energy gives information about the
vibrational modes of the sample.
Hyper-Raman spectroscopy
Very weak scattering at twice the laser frequency, 2v
0
, is called
Hyper-Rayleigh scattering. Similarly, Stokes and anti-Stokes hyper-
Raman scattering occur at 2v
0
v
vib
, where v
vib
is a vibration
frequency. The selection rules differ from those of Raman
scattering.

Electronic Raman scattering
Raman scattering can occur from electronic states, as well as
from vibrations. At room temperature the bands are very broad,
and merge into the background. At low temperatures (<80 K),
the bands sharpen, and give information about the energies of
electronic states of the molecule.

5000 6000 7000
0
800
1600
Part of electronic Raman spectrum of PrCl
6
3-
at 10 K
I
n
t
e
n
s
i
t
y
Raman shift (cm
-1
)
Books on Raman spectroscopy
There are many in CityU library, such as:
FT Raman spectroscopy, P. Hendra et al., Ellis
Horwood.
Raman and IR spectroscopy in biology and chemistry,
J. Twardowski and P. Anzenbacher, Ellis Horwood.

Also, there are some good short chapters:
Ch 18 in Skoog, Holler, Nieman, Principles of
Instrumental Analysis, Saunders.

Useful websites for Raman spectrometry
Great site covering all aspects
http://www.spectroscopynow.com/Spy/basehtml/SpyH/1,9076,6-0-0-0-0-home-0-0,00.html
Introduction to Raman spectroscopy
http://www-wilson.ucsd.edu/education/pchem/spectroscopy/sptyperaman.html
Analysis of pesticides and pharmaceuticals
http://www.aua.gr/georgiou/
From Encyclopaedia Brittanica: Raman
http://search.eb.com/bol/search?type=topic&query=Optical,+infrared,+and+Raman+spectroscopy&Dba
se=Articles&I3.x=44&I3.y=2
Andor Technology: good site comparing Raman and ir; FT-Raman and applications
http://www.andor-tech.com/ then click on Contents, then Raman on-line tour
Peter Griffiths website about FT
http://www.ftir.chem.uidaho.edu/
Raman analysis of olive oils (get the English page) by Adrian Shaw
http://pcjagg.dbs.aber.ac.uk/index.html
Study of molecular structures in supersaturated solutions
http://ihome.ust.hk/~keckchan/spectroscopy.html

Useful websites for Raman spectrometry

Instrument manufacturers
Thermo
http://www.spectroscopynow.com/Spy/basehtml/SpyH/1,1181,6-1-12-0-0-news_detail-0-3606,00.html

Renishaw instruments, do a search at
http://www.renishaw.com/client/start/index.asp

Bruker instruments
http://www.optics.bruker.com/
Nicolet instruments
http://www.nicolet.com/ and http://www.nicolet.com/labsys/products/Raman_theory.html

Jobin-Yvon instruments website
http://www.isa-gs.co.uk/

Scimedia company: about CCD camera detector
http://www.scimedia.com/english/camera/index.htm

ukap
www.anamap.co.uk