RAMAN SPECTROSCOPY

BY: Dr. Niha Ansari

NFSU
 INTRODUCTION
• A spectroscopic technique used to observe vibrational,
rotational, and other low-frequency modes in a system.
• Commonly used in chemistry to provide a fingerprint by which
molecules can be identified.
• It relies on inelastic scattering, or Raman scattering, of
monochromatic light, usually from a laser in the visible, near
infrared, or near ultraviolet range.
• Raman spectroscopy can give additional information about
lower frequency modes, and vibrations that give insight into
crystal lattice and molecular backbone structure.
 INTRODUCTION
• Raman spectroscopy was discovered by C. V. Raman in 1928.
• When the radiation pass through the transparent medium the
species present scatter a fraction of the beam in all direction.
• Raman scattering result from the same type of the quantities
vibration changed associated with IR spectra
• The difference in wavelength in between the incident and
scattered visible radiation correspond to wave length in mid IR
region.
• Raman spectroscopy is used to monitor crystallization processes
and reveal reaction mechanisms and kinetics. Combined with
analysis tools, this data enables informed reaction understanding
and optimization.
“ The Inelastic Scattering Of A Photon By Molecules
Which Are Excited To Higher Vibrational Or Rotational
Energy Levels.

”
It Was Discovered By C.V. Raman And K. S. Krishnan
DIFFERENCE BETWEEN
RAMAN & FTIR
 Raman spectroscopy FTIR spectroscopy
• Raman spectroscopy is an inelastic • Fourier transform infrared spectroscopy
scattering phenomenon the probes (FTIR) is a form of vibrational spectroscopy
molecular vibrations to provide a molecular that relies on the absorbance, transmittance or
fingerprint of materials. reflectance of infrared light. Using this
method, light is absorbed in different amounts
in a sample at distinct frequencies which
correspond to the vibrational frequencies of
the bonds in the sample.
• Raman spectroscopy depends on a change in • IR spectroscopy depends on a change in the
polarizability of a molecule. dipole moment.
• Raman spectroscopy measures relative • IR spectroscopy which measures absolute
frequencies at which a sample scatters frequencies at which a sample absorbs
radiation. radiation.
• Raman on the other hand is sensitive to • FTIR spectroscopy is sensitive to hetero-
homo-nuclear molecular bonds. For nuclear functional group vibrations and polar
example, it can distinguish between C-C, bonds, especially OH stretching in water.
C=C and C≡C bonds.
 SCATTERING
ABSORPTION
PHENOMENON
 THE RAMAN
SPECTROSCOPY
PRINCIPLE
When monochromatic radiation is incident PRINCIPLE
upon a sample then this light will interact
with the sample in some fashion. It may be
reflected, absorbed or scattered in some
manner. It is the scattering of the radiation
that occurs which gives information about
molecular structure
When light interacts with molecules in a
gas, liquid, or solid, the vast majority of the
photons are dispersed or scattered at the
same energy as the incident photons.
This is described as elastic scattering, or
Rayleigh scattering.
A small number of these photons,
approximately 1 photon in 10 million will
scatter at a different frequency than the
incident photon. This process is called
inelastic scattering, or the Raman effect.
Raman is based on scattering.
The sample is irradiated with a coherent
source, typically a laser. Most of the
radiation is elastically scattered (called the
Rayleigh scatter). A small portion is
inelastically scattered (Raman scatter,
composed of stokes and anti-stokes
portions).
The spectrum is measured with the laser line as a reference. Hence, the
peaks are measured as the shift from the laser line.
The peak positions are determined by the vibrational energies
associated with the bonds in the molecule(s) of which the sample is
composed. Because of this, the spectrum ends up looking very similar
to an IR spectrum and is interpreted similarly.
The bands that are emphasized in a Raman spectrum are those that
are due to highly polarizable bonds such as those with π electrons.
SCATTERING
• Scattering of light at the same frequency as incident light is
called RAYLEIGH SCATTERING
• Light scattered with different frequency is called RAMAN
SCATTERING
• The material absorbs energy and the emitted photon has a lower
energy than the absorbed photon Stokes Raman scattering
• The material loses energy and the emitted photon has a higher
energy than the absorbed photon Anti Stokes Raman
scattering
 RAYLEIGH SCATTERING
• Rayleigh scattering is the term used for elastic scattering of light by
molecules, and is by far the most dominant scattering process.
• The interaction does not change the energy state of the molecule and
as such the scattered photon has the same color (wavelength) as the
incident photon.
• In a Raman spectrometer, the Rayleigh scattered light has to be
removed from the collected light, otherwise it would obscure the
Raman signals.
 ANTI-STOKES RAMAN SCATTERING

• Anti-Stokes Raman scattering is another inelastic scattering process. Here,

a specific amount of energy is transferred from a molecular vibration to the
photon.
• The scattered photon has higher energy and a lower wavelength than
the incident photon. This process is even less likely to occur than Stokes
scattering.
• Therefore, it is usually not used in Raman spectroscopy.
• The information extracted from anti-Stokes scattered light is mostly
equivalent to the information extracted from Stokes scattered light, and only
very specialized applications will require the extra effort to measure both
scattering processes.
 STOKES RAMAN SCATTERING
• Stokes Raman scattering is the inelastic scattering process that transfers
energy from the light to a vibration of the molecule. Therefore, the
scattered photon has lower energy and a higher wavelength than the
incident photon.
• The amount of energy transferred is not arbitrary, it has to be exactly the
amount required to excite one of the molecular vibrations of the molecule.
The composition of the scattered light is therefore highly dependent on the
exact type of molecule (like a fingerprint).
• Stokes scattering is the most commonly exploited process to acquire a
Raman spectrum. It is, however, several orders of magnitude less likely to
occur compared to Rayleigh scattering, rendering it difficult to detect.
Summarizes The Scattering Processes Relevant For Raman
Spectroscopy:
 WHEN IS A MOLECULE RAMAN-
ACTIVE?
• Raman spectroscopy detects changes in the polarizability of a molecule.
It therefore only detects vibrations where the polarizability changes
during the movement (these are Raman-active vibrations)
• Polarizability describes how easily the electron cloud around a molecule
can be distorted.
• A change in polarizability is, for example, caused by an increase in the
size of the electron cloud.
• One example of a vibrational motion increasing the size of the (local)
electron cloud of a molecule is a symmetric stretching vibration .
• Raman spectroscopy occurs as a result of a molecular vibration causing a
"change in polarizability" of the molecule. In contrast, for a molecule to be
infrared active, the vibration must cause a change in the permanent dipole
moment.
• A simple case of a Raman Active molecule would be a species such as CS2. The
symmetrical stretch out and then in will be detected by Raman
spectroscopy. Since the molecule has no permanent dipole, this stretch would be
invisible in an infrared spectra.
• If a molecule has a center of symmetry, Raman active vibrations would not be
visible in the infrared. For example, the symmetric stretch of CS2 is Raman
active. The asymmetric stretches, which induce a dipole, are infrared active.
• As a result of this fundamental difference, it is often said that Raman and
Infrared Spectra are complementary, meaning that, between the two, the analyst
should be able to get a fairly complete picture of the vibrational modes of a
molecule.
INSTRUMENTATION
 RAMAN SYSTEM TYPICALLY CONSISTS OF
FOUR MAJOR COMPONENTS:

i. Excitation source (Laser)

ii. Sample illumination system and light collection optics
iii. Wavelength selector (Filter or Spectrophotometer)
iv. Detector (Photodiode array, CCD or PMT)
 1) SOURCE:
• The sources used in modern Raman spectrometry are nearly
always lasers because their high intensity is necessary to
produce Raman scattering of sufficient intensity to be measured
with a reasonable signal-to-noise ratio.
• Because the intensity of Raman scattering varies as the fourth
power of the frequency, argon and krypton ion sources that
emit in the blue and green region of the spectrum have and
advantage over the other sources.
 SAMPLE ILLUMINATION SYSTEM

• Liquid Samples: A major advantage of sample handling in

Raman spectroscopy compared with infrared arises because
water is a weak Raman scattered but a strong absorber of
infrared radiation. Thus, aqueous solutions can be studied by
Raman spectroscopy but not by infrared.
• This advantage is particularly important for biological and
inorganic systems and in studies dealing with water pollution
problems.
• Solid Samples: Raman spectra of solid samples are often
acquired by filling a small cavity with the sample after it has
been ground to a fine powder. Polymers can usually be
examined directly with no sample pretreatment.
• Gas samples: Gas are normally contain in glass tubes, 1-2 cm
in diameter and about 1mm thick. Gases can also be sealed in
small capillary tubes.
 SAMPLE ILLUMINATION SYSTEM
AND LIGHT COLLECTION OPTICS
• Light from the irradiated/illuminated spot is
collimated by a lens and guided to interference
filter or spectrometer to get Raman spectrum.
 WAVELENGTH SELECTOR (FILTER
OR SPECTROMETER):-
• Band pass filters are used to isolate a single laser beam.
• A combination of notch filter and high quality grating
monochromator is mostly employed in dispersive instruments.
• Double or even triple grating monochromators, super notch
filters, rejection filters, holographic notch or edge filters and
holographic filters are used to separate relatively weak Raman
lines from intense Rayleigh scattered radiations.
 DETECTOR (PHOTODIODE ARRAY,
CCD OR PMT):-
• Thermoelectrically cooled photomultiplier tubes and
photodiode array detectors were used in early models of
dispersive Raman spectrophotometers.
• Advances in instrumentation and technology replace these
detectors with more sensitive charge transfer devices (CTDs)
such as charge-coupled devices (CCDs) and charge-injection
devices (CIDs). These devices act as a detector and used in the
form of arrays.
• In CTD’s arrays, photosite converts the incoming optical
signal into charge which is integrated and transferred to
readout devices.
• Multichannel CCD detectors are used with laser
wavelengths of less than 1 μm while single element low
band-gap semiconductor such as Germanium (Ge) or
Indium–Gallium–Arsenic (InGaAs) detectors are used
with laser wavelengths of greater than 1 μm.
 CCD DETECTORS CHARGE-COUPLED DEVICES
• Most of the current dispersive Raman set-ups are now equipped
with multichannel two-dimensional CCD detectors.
• The main advantages of these detectors are:- The high quantum
efficiency. The extremely low level of thermal noise (when
effectively cooled). Low read noise.
• The large spectral range available.
• Many CCD chips exist, but one of the most common
spectroscopy sensor formats is the 1024 x 256 pixel array.
 APPLICATION
Raman Spectra of Inorganic Species
 The Raman technique is often superior to infrared for spectroscopy
investigating inorganic systems because aqueous solutions can be
employed.
 In addition, the vibrational energies of metal-ligand bonds are generally in
the range of 100 to 700 cm-1, a region of the infrared that is experimentally
difficult to study.
 These vibrations are frequently Raman active.
 Raman studies are potentially useful sources of information concerning
the composition, structure, and stability of coordination compounds.
Raman Spectra of Organic Species
• Raman spectra are similar to infrared spectra in that they have regions that are useful for
functional group detection and fingerprint regions that permit the identification of specific
compounds.
•Raman spectra yield more information about certain types of organic compounds than do
their infrared counterparts.

Quantitative applications
• Raman spectra tend to be less cluttered with peaks than infrared spectra. As a consequence,
peak overlap in mixtures is less likely, and quantitative measurements are simpler. In
addition, Raman sampling devices are not subject to attack by moisture, and small amounts
of water in a sample do not interfere.
Biological Applications of Raman Spectroscopy
 Raman spectroscopy has been applied widely for the study of biological systems.
 The advantages of his technique include the small sample requirement, the minimal
sensitivity toward interference by water, the spectral detail, and the conformational
and environmental sensitivity.