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Raman

Spectroscopy
Introduction
A vibrational spectroscopy
- IR and Raman are the most common
vibrational spectroscopies for assessing
molecular motion and fingerprinting species
- Based on inelastic scattering of a
monochromatic excitation source
- Routine energy range: 200 - 4000 cm
1


Complementary selection rules to IR
spectroscopy
- Selection rules dictate which molecular
vibrations are probed
- Some vibrational modes are both IR and
Raman active

Great for many real-world samples
- Minimal sample preparation (gas, liquid, solid)
- Compatible with wet samples and normal
ambient
Sir Chandrashekhara Venkata
Raman
November 7, 1888 November 21,
1970
Won the Noble Prize in 1930 for
Physics
Discovered the "Raman Effect"
Besides discovering the Raman Effect,
he studied extensively in X-Ray
diffractions, acoustics, optics,
dielectrics, ultrasonics, photo
electricity, and colloidal particles.
Raman discovered that the scattered radiation contained
photons not only of the same frequency as incident light, but
also a very small number of photons with changed or shifted
frequency (1 photon out of a million).
Selection Rules
Active in IR
To be visible in IR
vibration must change the
dipole moment of the
molecule
Active in Raman
To be visible in Raman
vibration must change the
polarizability of the
molecule
IR and Raman are both vibration spectroscopy techniques.
There is only one single common source of information
which can be obtained by both techniques. This source of
information is vibrations of atoms in molecules.
Raman and IR are complementary
techniques
H
2
, N
2
, O
2
, Raman active
Change of polarizability
change of polarisibility

change of electron density

change of electron cloud
Group assignments identify characteristic vibrational energy
Raman Spectroscopy: Classical
Treatment
Number of peaks related to degrees of freedom for N
atoms
DoF = 3N - 6 (bent)
Or
3N - 5 (linear) Selection rules related to symmetry

Rule of thumb: symmetric = Raman active
asymmetric = IR active

In the symmetric mode, there is no change in dipole
moment, therefore, IR inactive, while polarizability
fluctuates, Raman active.
In the asymmetric, change in dipole moment, thus IR
active, but polarizability remains the same, Raman inactive.
extended
compressed
Raman: 1335 cm
1

IR: 2349 cm
1

IR: 667 cm
1

CO
2

Raman + IR: 3657 cm
1

Raman + IR: 3756 cm
1

Raman + IR: 1594 cm
1

H
2
O
equilibrium
IR vs Raman Spectroscopy
IR and Raman are both useful for Fingerprinting

















Symmetry dictates which are active in Raman and IR
Raman
Raman spectroscopy is
SCATTERING spectroscopy.
Scattering involves a
momentary distortion of the
electrons distributed around a
molecular bond. Thus, the
molecule is temporarily
polarized.
For example, H
2
and N
2
can
be detected.
IR vs Raman Spectroscopy
IR
IR spectroscopy is
ABSORPTION spectroscopy
Requires the vibrational mode
of the molecule to have a
change in the dipole moment
or charge distribution
associated with it. Only then,
radiation of same frequency
interact with the molecule, and
promote it to the excited state.
Sample preparation is required
in most cases.
What Exactly Is Being Measured?
METHANE
When light hits a
sample, it is
excited, and is
forced to vibrate
and move. These
vibrations which we
are measuring.
Why Raman?
In Raman spectroscopy,
by varying the frequency of
the radiation, a spectrum
can be produced, showing
the intensity of the exiting
radiation for each
frequency.
This spectrum will show
which frequencies of
radiation have been
absorbed by the molecule
to raise it to higher
vibrational energy states.
Rayleigh scattering most photons are elastically scattered.
emitted photon has the same wavelength as
the absorbing photon
Stokes scattering energy of the scattered radiation is less than
the incident radiation
anti-Stokes scattering energy of the scattered radiation is more
than the incident radiation
Stokes vs. Anti Stokes
If light is not absorbed the
majority of the photons
pass through the sample
by means of Rayleigh
Scattering
Some of the photons
(~1/10,000,000) will pass
through the sample and
undergo Stokes Scattering
Even fewer photons will
pass through the sample
and undergo Anti-Stokes
Scattering
Raman efficiency (Stokes)
Rayleigh
Raman
Raman spectroscopy requires a monochromatic
and highly intense source (laser)
Raman scattering: 1 in 10
6
-10
10
photons
Using Stokes/Peaks to Determine
Vibrations
Stokes and anti-Stokes lines are equally displaced from the
Rayleigh line.
anti-Stokes line is much less intense than the Stokes line
because only molecules that are vibrationally excited prior to
irradiation can give rise to the anti-Stokes line.
Hence, only the more intense Stokes line is normally measured.
Raman spectrum
Raman spectrum of sulfur
Raman shift
n
Raman shift
= n
Laser
- n
scattered
Wavenumber n shift is defined as the difference in
wavenumbers (cm
-1
) between the observed radiation and that
of the source.
514.5nm
Fluorescence
Fluorescence is the emission of a photon by a molecule following
its excitation by an electromagnetic radiation of a precise
wavelength.
This excitation induces an energy jump from a fundamental
electronic state S
0
to an upper electronic energy level S
1
.
The molecule comes back to its fundamental energy level while a
photon is emitted.
The photon energy corresponds to the energy difference
between the two levels S
0
and S
1
Some small energy losses are due to internal conversion among
the different vibrational and rotational levels of each electronic
state of the molecule.
That's why E
1
(excitation energy) is always greater than E
2
(emission energy)
E
1
= hc and E
2
= hc , so
1
<
2

1

2
Fluorescence is common in many organic materials, but
also in impure inorganic materials.
Fluorescence does no affect the Raman effect. However,
since the fluorescence spectrum is much stronger and
broader than the Raman spectrum, the Raman spectrum
may disappear under the fluorescence background.
Using different excitation wavelength to eliminate fluorescence
Effect of excitation wavelength
Fluorescence vs Raman
Raman Spectrometers
Raman spectrometers basically employ one of
two technologies for the collection of spectra
1- Dispersive Raman
2- Fourier Transform Raman (FT- Raman)
Each technique has unique advantages and
each is ideally suited to specific analyses
Dispersive Raman Spectroscopy
To separate the collected Raman scattered light into
individual wavelengths, the Raman signal is focused
onto a grating that separates the light into the
different frequencies.
Then, the dispersed beam is directed to the CCD
(charged-coupled devices) detector to be collected.
FT- Raman
Consists of an excitation laser (longer wavelength),
an interferometer and high sensitivity detector.
Interferometer produces interferogram which
encodes the unique frequencies of the Raman
scattering into a single signal.
How does FT-Raman work?
Vibrational spectra are presented as frequency
spectra, which are then decoded using Fourier
transformation mathematical techniques, and finally
the desired spectral information is presented.
Dispersive vs. FT-Raman
Feature Dispersive FT-Raman
Available
Wavelength
<200nm to 850nm 1064nm
Fluorescence More fluorescence
(Except UV)
Better
fluorescence
avoidance
Detector CCD Ge or GaAs
Best Spectral
Resolution
Typically 1-4 cm
-1
~0.5cm
-1
Raman techniques Couple Raman
spectroscopy with a microscope
Confocal Raman Spectroscopy
Why?
Allows analysis of very small
samples
Distinguish the substance of
interest from its surrounding.

How does it work?
By focusing the laser beam
onto the sample, and passing
the returning beam into the
system for analysis and
detection.
Surfaced enhanced Raman spectroscopy (SERS)
Tip enhanced Raman spectroscopy (TERS)
Resonance Raman spectroscopy
Spatially Offset Raman Spectroscopy
Hyperspectral Raman Mapping
Raman tomography
Raman imaging
Coherent anti-stokes Raman spectroscopy (CARS)
Stimulated Raman spectroscopy
Other Raman Techniques
Applications Carbon Allotropes
Applications Art Restoration
This 12th century fresco on a
church wall in Italy needed to be
restored. What paints to use?
Raman analysis clearly identified
the paints and pigments that
were originally present,
permitting a correct choice of
cleaning materials and
subsequent repainting to restore
its original condition.
Forensic analysis of paint chips in vehicle accidents. Often
multiple layers. Can analyze with IR by stripping successive
layers. Image edge with microRaman.
Applications Paint Chips
Layers 1 and 3 turned out to be rutile phase
TiO
2
a white paint. Layer 2 was a Goethite,
a red pigment and corrosion inhibitor. Layer 4
was molybdate orange, a common red paint
in the 70s in North America and still used in
the U.K. today. Layer 5 was a silicate based
paint.
In 1999 a new process was developed called GE POL
whereby brown type IIa diamonds could be treated to
become indistinguishable from naturally clear
diamonds. Raman presented way to distinguish them.
Applications Gem Forgery
Originally brown
diamond
Naturally clear
diamond
Identify poly(carbonate) from poly(methylmethacrylate).
Both used for shatter-proof glass
Applications Bullet Proof Glass
Here are the spectra of 5
common sunscreen ingredients.
Raman is able to determine from
a spectrum on the arm the nature
of the sunscreen being used.
A: ODPABA (octyl N,N-dimethyl-
paminobenzoic acid)
B: OMC (octyl p-
methoxycinnamate)
C: BZ3 (oxybenzone)
D: OCS (octyl salicylate)
E: DBM (dibenzoylmethane)
Applications Sunscreen Formulations
Raman Instruments
Advantages and disadvantages
Little sample preparation (Polishing and fixing to a
slide is common)
Not sensitive to water (Good for biological samples)
High chemical specificity (Narrow spectral bands)
Qualitative and Quantitative information
Non-destructive (A measurement does not
chemically or physically change the sample)
Can take measurements on solids, liquids, or gases
Measurements are taken without touching the
sample (Remote sensing)
Easily coupled with fiber-optics
Advantages
Acquisition times tend to be longer than other techniques
Raman signal tends to be weak
Raman signal is often mixed with a fluorescent background
signal, which can make signal processing difficult.
High laser powers and burn delicate samples
More expensive
Disadvantages
Summary
1. Raman is a vibrational spectroscopy akin to IR
- Good for fingerprinting, probing molecular symmetry

2. Scattering-based, not transmission/reflection
- Means no need for fancy sample preparationgas, liquid,
or solid
- Virtually always use Stokes lines due to stronger signal

3. You need to pick excitation energy (laser line)
- 785 nm: Fluorescence less probable; Lower Raman signal
- 514 nm: Fluorescence more probable; Resonance more
likely; Higher signal
Raman spectroscopy is inelastic scattering of light
from vibrational modes of molecules/solids
Vibrational frequencies are in the IR region
Both IR and Raman are fingerprint techniques:
each molecule has its own characteristic
vibrational spectrum
Lasers are convenient sources to excite Raman
Spectra
We need a monochromator to disperse the light
scattered from the sample, and a sensitive
detector to detect the feeble Raman signal
http://www4.hcmut.edu.vn/~huynhqlinh/qpys/FTIR-
Raman/Raman%20Spectroscopy.htm
http://www.sicklecellinfo.net/raman.htm