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Raman Spectroscopy
It is discovered by Indian physicist C.V. Raman in
1928 (Nobel Prize in Physics, 1930)

Raman noted that the wavelength of small fraction of

scattered radiation by certain molecules differs from
that of the incident beam.

The shifts in wavelength depend upon the chemical

structure.

The phenomenon of Raman scattering results from

the same type of quantized vibrational changes that
are associated with IR absorption.

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The difference in wavelength
UNIVERSITY OF THEbetween the incident
PHILIPPINES and
MANILA
scattered radiation corresponds to wavelengths in the
mid-IR region.
Thus, the Raman spectrum and IR spectrum for a given
species often resemble one another quite closely.

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However, distinct differences between the two exist to
make these techniques complementary rather than
competitive.

Example: Raman spectrum is more useful for highly

symmetric molecules.
Important advantages of Raman over IR
Water does not cause interference in Raman.
Unlike in IR, aqueous solution of sample can be used.

Glass or quartz cells can be employed.

Use of NaCl and atmospherically unstable windows is avoided.

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Disadvantages of Raman
Spectrum was hard to obtain before lasers became
available in 1960s.
Fluorescence of sample or impurities interfere with
Raman.
This is now overcome by the use of IR laser source and
Fourier transform spectrometers.

Theory of Raman Spectroscopy

Raman spectra are obtained by irradiating a sample with
a laser source of visible or IR radiation.
During irradiation, the spectrum of scattered radiation
is measured at some angle (usually 90 deg)
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The intensities of Raman lines are 0.001% of the
intensity of the source.
This makes their detection and measurement difficult.

Raman Spectra

Portion of Raman
spectrum of CCl 4
excited by Ar ion laser
having a wavelength of
488.0 nm

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The scattered radiation is of three types:
Stokes, anti-Stokes, and Rayleigh

The Rayleigh radiation has wavelength exactly the same

as that of the excitation source and is significantly more
intense than the other two.

In Raman spectra, the abscissa is the wavenumber shift,

Δν - the difference in wavenumbers (cm-1) between
the observed radiation and the source.
In the CCl4 spectrum, three peaks are found on either
side of the Rayleigh peak and the pattern of the shifts
are identical.
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Stokes lines are found at wavenumbers that are 218,
314, and 459 cm-1 smaller than the Rayleigh peak.
anti-Stokes lines occur at 218, 314, and 459 cm-1 greater
than the wavenumber of the source.

The magnitude of Raman shifts are independent of the

wavelength of excitation.
- similar spectrum would be obtained using Kr, He:Ne or a Nd:YAG
laser

Raman spectral lines at lower energies is analogous to

Stokes shifts found in fluorescence.
For this reason, negative raman shifts are called Stokes shifts.

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Shifts toward higher energies are termed anti-Stokes.
anti-Stokes lines are appreciably less intense than the
corresponding Stokes lines.
- for this reason, only the Stokes part is generally used.

The abscissa of the Raman spectrum is often labeled

simply frequency (cm-1) not wavenumber shift and the
negative sign is usually omitted.
Fluorescence may interfere seriously with Stokes shifts
but not with anti-Stokes shifts.
With fluorescing samples, anti-Stokes signals may be more useful
despite their lower intensities.

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Mechanism of
Raman and Rayleigh
Scattering
The process is not
quantized, the E of
the molecule can
assume any of the
infinite number of
values or states
called virtual states.

Thicker lines indicate higher

probability of occurrence at RT.

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The thin (green) arrows show the type of change when
the molecule happens to be in the first vibrational level
of the electronic ground state.

- at RT, the fraction of molecules in this state is small,

and the probability of the above process is small.

The Rayleigh scattering has greater probability; there is

no loss of energy (Eexcitation = Escattered radn) i.e. the
collision is elastic.

The Stokes and the anti-Stokes differ from Rayleigh

radiation by ±ΔE, the energy of the first vibrational
level in the g.s.
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If the bond were IR active, the E of absorption would
also be ΔE.
- the Raman frequency shift and the IR absorption peak
frequency are identical.

The relative populations of the two E states are such

that Stokes is favored over anti-Stokes.

However, the ratio of anti-Stokes to Stokes intensities

will increase with temperature.
- larger fraction of the molecule will be in the first
vibrationally excited state at high T.
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Wave Model of Raman and Rayleigh Scattering
Assume that a beam of radiation having a frequency νex is
incident upon a solution of an analyte.

The electric field of radiation is given by

E = E o cos(2πν ex t )
where Eo is the amplitude of the wave, vex is excitation wavelength

When the electric field of the radiation interacts with the

electron
€ cloud of an analyte bond, it induces a dipole
moment, m, in the bond that is given by
m = αE = αE o cos(2πν ex t )
where α is a proportionality constant called the polarizability of the bond.
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Polarizability is a measure of the deformability of a
bond in an electric field.

In order to be Raman active, the polarizability of a bond

must vary as a function of the distance between nuclei
according to the equation
 ∂α 
α = α o + ( r − req ) 
 ∂r 
where αo is the polarizability of the bond at the equilibrium
internuclear distance, req; and r is the internuclear distance
at any instant.
€
The change in internuclear distance varies with the
frequency of vibration νv as given by
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r − req = rm cos(2πν v t )
where rm is the maximum internuclear distance relative to
the equilibrium.

Thus€polarizability becomes
 ∂α 
α = α o +  rm cos(2πν v t )
 ∂r 
Since induced dipole moment, m is
m = αE o cos(2πν ex t)
€
Substitution of α gives
 ∂α 
€m = α o E o cos(2πν ex t) + E o rm  ∂r  cos(2πν v t)cos(2πν ex t)

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Recall that
cos x cos y = [cos(x + y) + cos(x − y)] / 2

Applying this identity gives

€ E o  ∂α 
m = α o E o cos(2πν ex t) + rm   cos[2π (ν ex − ν v ) t ]
2  ∂r 
E o  ∂α 
+ rm   cos[2π (ν ex + ν v ) t ]
2  ∂r 
The first term in this equation represents Rayleigh
scattering, which occurs at the excitation frequency, νex
€
The second and third terms correspond to the Stokes
and the anti-Stokes frequencies.
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Note that Raman scattering requires that the
polarizability of a bond varies as a function of distance.
∂α must be greater than zero if a Raman line is to appear
∂r
Raman scattering involves a momentary distortion of
electrons distributed around a bond, followed by the
reemission of radiation as the bond returns to its g.s.
In its distorted form the molecule is temporaily
polarized (i.e. it develops momentarily an induced
dipole).
The induced dipole disappears upon relaxation.

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For example, the homonuclear molecules such as N2, O2
or H2 has no dipole moment either in the equilibrium or
at any instant during stretching vibrations.

N N O=O H-H
N N O O H H
μ= qr = 0 μ= qr = 0 μ= qr = 0
The stretching mode is IR inactive in these
molecules.
On the other hand, the polarizability of the bond
between the two atoms of such a molecule varies
periodically in phase with the stretching vibrations.
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α N N O =O H-H
increases
N N O O H H

The stretching mode has a corresponding Raman

line in the spectrum.

Example:
O=C=O O=C=O
symmetric stretch asymmetric stretch

IR inactive IR active
Raman active Raman inactive
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Raman Depolarization Ratios

The 459 cm-1 line in

CCl4 spectrum has
depolarization ratio of
0 . 0 0 5 , i n d i c at i n g
m i n i m a l
depolarization - said
to be polarized.
- due to symmetric
breathing

Nonsymmetrical vibrations is
close to max of 6/7 (or 0.86).
- the 218 and 314 lines in CCl4 has
p = 0.75

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Instrumentation

Three Components:

1. Laser source

2. Sample-illumination
system
3. Suitable spectro-
photometer

Two sample excitation systems

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Sources
Helium/Neon Laser
- most widely used; principal line is 632.8 nm

Argon ion Laser

- used when higher sensitivity (3x) is required;
principal lines are 488.0 and 514.5 nm

Nd:YAG Laser
- emits NIR at 1.064 μm
- can be operated at higher power (up to 50W) without
causing photodecomposition of the sample
but partially offset by “Raman α ν4” relationship
- not energetic enough to bring about electronic
transitions (can’t cause fluorescence)

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Sample Illumination System
Sample handling for Raman is simpler than for IR.

- glass can be employed for windows, lenses, etc.

instead of moisture-sensitive halides

- laser source can be focused on a small sample area

(very small samples can be readily examined)

- common sample holder for liquid is an ordinary

glass melting-point capillary.

- water is a weak Raman scatterer but a strong

absorber of IR radiation.
- aqueous solutions can be studied by Raman but
not IR spectroscopy.

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Fourier Transform Raman Spectroscopy

A major limitation to Raman spectroscopy is backgroud

signal arising from fluorescence of analyte or impurities.

- Raman scattering has low efficiency

- for an incident flux of 108 photons, on average,

only one is Raman scattered;
- if an impurity with ppm-level absorptivity and quantum
yield of 0.1 is present, 10 fluorescent photons could be
produced.

It is impossible to obtain a meaningful Raman

spectrum with a highly fluorescent impurity or a
weakly fluorescent sample.

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Sample Raman Spectrum (of Anthracene)

- obtained with
conventional Raman
- most of the recorded
signal arises from
fluorescence

- recorded with an FT
spectrometer
- note the total
absence of
fluorescence
background signal

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Optical Diagram of FT Raman Spectrometer

- the interferometer is the same as is used in IR

- the detector is Ge photoconductor
- cut-off filters are employed to detect only the Stokes
portion of the spectrum
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Applications of Raman Spectroscopy
Inorganic Species
Raman technique is often superior to IR for investigating
inorganic systems because aqueous solutions can be
employed.

- metal-ligand bonds are generally in the range 100 - 700 cm-1, a

region in IR that is difficult to study but Raman peaks with
wavenumber shift values in this range are readily observed

Organic Species
Raman spectra are similar to IR (i.e. they have FGR and FPR)
Raman spectra yield more information about certain types
of compounds.
- double bond stretch in olefin is weak in IR but intense in Raman.

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Quantitative Applications

Raman spectra tend to be less cluttered with peaks than IR

spectra are.
- peak overlaps in mixtures are less likely; quantitative
measurements are simpler.

Small amounts of water do not interfere.

Quantitative analysis on very small samples is possible.
- laser microprobes are employed for this work.

Laser microprobes applications:

- determination of analytes in single bacterial cells.
- determination of components in individual particles of smoke.
- determination of species in microscopic inclusions in minerals.

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Resonance Raman Spectroscopy
Resonance Raman scattering refers to a phenomenon in
which Raman line intensities are enhanced by excitation
with wavelengths that closely approach that of an electronic
absorption peak of an analyte.

Raman peaks are enhanced by a factor of 102 to 106

LOD becomes as low as 10-8 M (in contrast to normal

Raman’s LOD of 0.1 M)

In resonance Raman, the electron is promoted to an excited

electronic state followed by an immediate relaxation to the
vibrational level of the electronic ground state.
It differs from fluorescence in that relaxation to the ground
state is NOT preceded by prior relaxation to the lowest
vibrational level of the excited electronic state.

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Energy Diagram

Resonance Raman Fluorescence

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