Molecular Vibrational

Spectroscopy

RAMAN SPECTROSCOPY
 Historical Background
• First postulated by
Smekal in1923
• First observation of
Raman Scattering by
Sir V. C. Raman in
1928
• Won the Noble Prize
in 1930 in Physics

Dr. Chandrashekhara Venkata Raman

1888 - 1970
 Sir V. C. Raman
1928, he discovered
• Visible wavelength of a small fraction of
the radiation scattered by certain
molecules differs from that of incident
radiation
• The shifts in the wavelength depend on
the chemical structure of the molecule
responsible for the scattering
 Overview
A vibrational spectroscopy
• IR and Raman are the most common
vibrational spectroscopies for assessing
molecular motion and fingerprinting
species
• Raman is based on inelastic scattering
of a monochromatic excitation source
• Routine energy range: 50 - 4000 cm –1
 Raman Basics
• Raman spectroscopy studies the frequency change of
light due to the interaction with matter.
• The energy of a vibrational mode depends on molecular
structure and environment (atomic mass, bond order,
molecular substituents, molecular geometry and
hydrogen bonding)
• Raman signal is weaker than incident light.
• Photons are not absorbed
• To observe Raman scattering the molecule must be
polarizable.
 Polarizability
• The relative tendency of a charge
distribution, like the electron cloud of an
atom or molecule, to be distorted from its
normal shape by an external electric field
which may be caused by the presence of
a nearby ion or dipole.
 Raman scattering
• Results from the same type of quantized
vibrational changes associated with IR
absorption
• The difference in wavelength between and
scattered visible radiation corresponds to
wavelengths in the MIR region
• IR scattering spectra and IR absorption spectra for
a given species resemble one another closely
 Theory
• Irradiate a molecular sample with a
powerful monochromatic laser source of
visible or NIR radiation
• The intensities of Raman lines are 0.001%
of the intensity of the radiation source
– More difficult to detect and measure Raman
bands compared to IR bands
– Very sensitive detectors are now available
 Figure 18-1

Resulting Raman Spectrum

Intensity of Raman lines are 0.001% intensity

of the source

Probability of Emission and Observed Intensity

Raleigh scattering >> Stokes >> anti-Stokes
difference in population of energy levels of vibrational transitions
 Figure 18-1
Stokes scattering
• Lower frequency emissions
Anti-Stokes scattering
• Higher frequency emissions
 Figure 18-1
Rayleigh scattering is
• an elastically scattered radiation
• of the same frequency as the excitation
beam
 Excitation of Raman
• The molecule at ground vibrational state
( = 0) is irradiated by a monochromatic
beam of energy h ex
• The molecule absorbs the radiation of
energy h ex and is promoted to a ‘virtual’
state of energy level of j
 Stokes scattering
The molecule at the virtual state
• reemits a photon of energy h(ex - v)
• the scattered radiation is of a lower
frequency than the excitation radiation
Anti-Stoke
scattering
• Molecules in vibrationally excited state ( =
1) can also be promoted to the virtual state of
energy level j
– The population of molecules at this energy level
is lower
• Scatter radiation inelastically
• Reemits photon of energy h(ex + v)
• The scattered radiation is of a higher
frequency than the source radiation
 Frequency shifts
Anti-Stokes Raman lines
• (ex + v) - ex = +v
Stokes Raman lines
• (ex - v) - ex = -v
Both correspond to vibrational frequency, v
Stokes lines are more intense than anti-Stokes
lines
• Ground vibrational level ( = 0) is more highly
populated than the excited vibrational level ( = 1)
 Raman spectrum
A complete Raman spectrum consists of
• A Rayleigh scattered peaks
– High intensity, same wavelength as excitation
• A series of Stokes-shifted peaks
– Low intensity, longer wavelength
• A series of anti-Stokes shifted peaks
– Still lower intensity, shorter wavelength
 Raman spectrum of CCl4
• Laser source 488.0 nm
• Abscicca is the wavelength shift,  
• The difference in wavenumber (cm-1)
between the observed radiation and that
of the source
• Raman lines on both sides of Rayleigh line
are identical
 Raman spectrum of CCl4
Stokes lines are given
positive values

Wavenumber shift

    ex   v

• excited by 488.0 nm laser radiation.

(The number above the peaks is the Raman shift.)
3 Raman lines
• Rayleigh: 488 nm = 20,492 cm-1
• Stokes lines; 218, 314 and 459 cm -1
smaller than wavenumber of the source
• Anti-Stokes lines; 218, 314 and 459 cm -1
greater than wavenumber of the source
• Stokes lines are more intense than anti-
Stokes
 Stokes lines
Only Stokes lines are used
• Rayleigh does not offer information on the
structure
• Anti Stokes lines are less intense
 Raman spectrum
• The abscissa is labeled as wavenumber,
cm-1.
• Independent of the wavelength of
excitation
– Different laser sources produce the same
spectrum
Raman scattering

energy absorbed by
molecule
from photon of light
is not quantized

IR absorbance
 Rayleigh and Raman scattering

Infinite number of
virtual states

energy absorbed by
molecule
from photon of light
is not quantized
 Some scattered emissions occur at the
same energy while others return in a
different state

Rayleigh Scattering Raman Scattering

no change in energy net change in energy
h in = h sc h in </> h sc

Elastic: collision between photon and molecule results in no change in energy

Inelastic: collision between photon and molecule results in a net change in energy
 Two Types of Raman Scattering

Anti-Stokes: E = h + E

Stokes: E = h - E

E
• The energy of the first vibration level of the ground state
• IR vibration absorbance

Raman frequency shift and IR absorption peak frequency are identical

 Selection rule
Complementary selection rules to IR
spectroscopy
• Selection rules dictate which molecular
vibrations are probed
• Some vibrational modes are both IR and
Raman active
• Selection rules related to symmetry
Rule of thumb: symmetric=Raman active
asymmetric=IR active
 Rule of mutual exclusion
• If a molecule has a center of symmetry then
Raman active vibrations are infrared inactive,
and vice versa.
Raman Spectroscopy
Raman spectroscopy: complementary to IR spectroscopy.
- radiation at a certain frequency is scattered by the molecule
with shifts in the wavelength of the incident beam.
- observed frequency shifts are related to vibrational changes in the
molecule  associated with IR absorbance.
- Raman scattering spectrum resembles IR absorbance spectrum
- Raman and IR mechanisms differ

Comparison of Raman and IR:

IR Raman
i. vibrational modes vibrational modes

ii. change in dipole change in polarizability

extend compress

- + -
iii. excitation of molecule to momentary distortion of the
excited vibrational state electrons distributed around the bond

iv. asymmetric vibrations (active) symmetric vibrations (active)

 Polarizability
• A measure of the electron cloud around a
molecule can be distorted
• If a vibration does not greatly change the
polarizability,
– the polarizability derivative will be near zero
– the intensity of the Raman band will be low.
• The vibrations of a highly polar moiety,
such as the O-H bond, are usually weak.
 Active Raman Vibrations:
- need a change in polarizability of molecule during vibration
- polarizability related to electron cloud distribution

IR & Raman are complimentary.

There are cases where vibration is both IR & Raman active (eg. SO 2, a
non-linear molecule)

In general: O

IR tends to emphasize polar functional groups (R- C

OH, , etc.) – strong absorbers

Raman emphasizes aromatic and carbon backbone (C=C,
-CH2-, etc.)
Raman can use with aqueous samples – advantage over IR
Raman frequency range: 4000 - 50 cm-1(Stokes and anti-Stokes)
 Condition for Raman Spectroscopy
Vibrational modes that are more polarizable are more Raman-active

Examples:

N2 (symmetric stretch)
•Cause no change in dipole moment (IR-inactive)
•Cause a change in the polarizability of the bond as the bond gets longer it is more
easily deformed (Raman-active)

CO2 (asymmetric stretch)

-cause a change in dipole moment (IR-active)
-polarizability change of one C=O bond lengthening is cancelled by the shortening of
the other- no net polarizability (Raman-inactive)
 Typical strong Raman scatterers
• moieties with distributed electron clouds
– Example:carbon-carbon double bonds.
– The pi-electron cloud of the double bond is easily
distorted in an external electric field.
Bending or stretching the bond
• changes the distribution of electron density
substantially
• causes a large change in induced dipole
moment.
 IR-active vs. Raman active
IR-active: dipole moment change
N2, O2, etc: IR inactive, but Raman active

Raman active: polarizability

change
Comparison: IR and Raman
Symmetrical stretch
• IR inactive, Raman active
• Zero net dipole moment as the
two O atoms move away or
toward the central C atom
Asymmetrical stretch
• IR active, Raman inactive
• As polarizability of one of the
bond increases as it
lengthens, the polarizability of
the other decreases
– No net change in the molecular
polarizability
 Raman Spectrometer
• Probes ro-vibrational structures of molecules
• Samples - gases, liquids and solids
• Shift back from FT-Raman to dispersive Raman
with multi-channel detector systems
– FT-Raman suffers from heating and low sensitivity
problems
• Resurgence in recent years due to
– Development of new detectors with improved
sensitivity
– The use of laser as the radiation source
– Moderate cost (RM 500,000)
Why Raman is making a comeback
Instruments of the past
• Large (occupy entire lab)
• Complex
• Difficult to maintain
• Required a dedicated operator
Modern instruments
• Integrated and compact (bench top)
• Easy to use
• Low maintenance
 Raman spectrometers
Types of Raman spectrometers
• Dispersive Raman
• FT Raman (interferometer)
• Resonance Raman
• Surface Enhanced Raman Spectroscopy (SERS)
– enhancement factor 104 to 107
• SERRS
– enhancement factor 105 to 108
Dispersive Raman spectrometer
 Raman spectrometer
Components of instrument
• Excitation source – LASER
• Sample
• Filter – to remove Rayleigh scattering
• Grating monochromator – Echelle
• Detector – charged coupled device (CCD)
– Highly sensitive detector
 Raman Instrumentation
Sample
cell

Monochromator Radiation
transducer

Computer
data system

Laser
source
Schematic diagram of Raman
spectrometer
 Energy conditions to generate normal
Raman vibrational spectra
• An incident photon must have an energy
substantially larger than that required to
excite vibration.
• The incident photon must have less energy
than is needed to produce electronic
excitation.
Both conditions are satisfied by wavelengths
in the visible/near–IR region.
• 532, 633 and 780/785 nm
 Radiation source
A laser
• to get required intensity of light for
reasonable S/N
– Raman scattering is only 0.001% of radiation
source
 Visible region
• visible laser source is used because of
high energy and intensity
• allows use of glass/quartz sample cells
and optics
• UV/Vis type detectors
 Light Source
Common Laser Sources for Raman Spectroscopy

Near IR :
(1) Can be operated at much higher power without causing
photodecomposition of the sample.
(2) Not energetic enough to populate a significant number of fluorescence-
producing excited electronic state.
 Detectors
UV-Visible Region:
• Cooled Photomultiplier Tube
• CCD
• Photodiode arrays
Near IR Region:
• Germanium Transducer
Simpler than IR spectroscopy
• glass can be used as optical
component materials in Raman.
• Laser source is easily focused on a
small sample area and emitted
radiation efficiently focused on a slit.
 Comparison of Raman and IR spectra
for mesitylene and indene

1. Several peaks have identical IR abs  and Raman Δ.

2. The relative size of the corresponding peaks is quite different.
3. Certain peaks present in one spectrum but absent in the other spectrum.
 Sample handling
Simpler than IR
• Glass can be used for windows, lenses and
other optical components
– IR spectrometers require more fragile and
atmospherically unstable halide salts
• Laser source can be focused on a small
sample area
• The emitted radiation is efficiently focused on
the slit
 Gas samples
• Gases are contained in glass tubes 1 – 2
cm in diameter and 1 mm thick
 Liquid samples
• Sealed in ampoules, glass tubes or
capillaries
• Aqueous solutions can be studied
– Strong IR absorber
 Solid samples
• As powders
• Polymers are examined directly without
sample pretreatment
 Applications of Raman
spectroscopy
a) Qualitative Information
i. characteristic regions for different functional groups as in IR
ii. Raman correlation charts available
iii. Good for aqueous based samples
iv. Useful for a variety of samples, organic, inorganic & biological
b) Quantitative Information – not routinely used
i. fewer technical problems than IR, fewer peaks
ii. Interference from fluorescence
iii. Higher cost
iii. Signal weak – require modified Raman methods
1) Resonance Raman spectroscopy allows detection of 10 -3 - >10-7 M by using
lasers light with wavelength approaching electronic absorption
2) Surface enhanced Raman spectroscopy (SERS) places samples
on metal or rough surfaces that increase Raman scattering
 Advantages
• Can be used with solids, liquids or gases.
• No sample preparation needed
• Spectra from each material are unique, can be
used to identify materials conclusively
• Non-destructive
• No vacuum needed unlike some techniques,
which saves on expensive vacuum equipment
• Short time scale. Raman spectra can be acquired
quickly.
• Can work with aqueous solutions (infrared spectroscopy
has trouble with aqueous solutions because the water
interferes strongly with the wavelengths used)
• Glass vials can be used (unlike in infrared spectroscopy,
where the glass causes interference)
• Can use fiber optic cables for remote sampling
• Fast analyses
 Disadvantages
• Cannot be used for metals or alloys.
• The Raman effect is very weak, which leads to low
sensitivity, making it difficult to measure low
concentrations of a substance. This can be countered by
using one of the alternative techniques (e.g. Resonance
Raman) which increases the effect.
• Some materials may fluorescence
• Samples with color may absorb laser light and burn.
• Expensive