RAMAN SPECTROSCOPY

Introduction
A large variety of spectroscopic techniques are available for the analysis of materials and
chemicals. Among these is Raman spectroscopy. This relies on Raman scattering of light by a
material, where the light is scattered inelastically as opposed to the more prominent elastic
Rayleigh scattering. This inelastic scattering causes shifts in wavelength, which can then be
used to deduce information about the material. Properties of the material can be determined
by analysis of the spectrum, and/or it may be compared with a library of known spectra to
identify a substance.

Since the discovery of Raman scattering in the 1920s, technology has progressed such that
Raman spectroscopy is now an extremely powerful technique with many applications.

Raman scattering

Raman scattering (sometimes called the Raman effect) is named after Indian physicist C. V.
Raman who discovered it in 1928, though predictions had been made of such an inelastic
scattering of light as far back as 1922. The importance of this discovery was recognised even
then, and for his observation of this effect Raman was awarded the 1930 Nobel Prize in
Physics. This was and remains the shortest time from a discovery to awarding of the Prize. In
fact, Raman was so confident that he arranged his travel to Stockholm several months in
advance of the recipients being announced! This confidence seems quite justified, given that
within a year and a half of his discovery, more than 150 papers mentioning the effect had
been published. Since then, Raman scattering has given rise to a number of important
technologies, and foremost among these is Raman spectroscopy.

Most light passing through a transparent substance undergoes Rayleigh scattering. This is an
elastic effect, which means that the light does not gain or lose energy during the scattering.
Therefore, it stays at the same wavelength. The amount of scattering is strongly dependent on
the wavelength, being proportional to λ-4. (It is this fact that makes the sky blue, the shorter
wavelength blue components in the Sun’s light are Rayleigh scattered in the atmosphere far
more than the longer wavelengths. Blue light is then seen coming from all over the sky. The
scattering of blue light from its direct path from the Sun also causes the Sun itself to appear
yellow.)

In Rayleigh scattering a photon interacts with a molecule, polarising the electron cloud and
raising it to a “virtual” energy state. This is extremely short lived (on the order of 10 -
14
 seconds) and the molecule soon drops back down to its ground state, releasing a photon.
This can be released in any direction, resulting in scattering. However, since the molecule is
dropping back to the same state it started in, the energy released in the photon must be the
same as the energy from the initial photon. Therefore, the scattered light has the same
wavelength.

Raman scattering is different in that it is inelastic. The light photons loose or gain energy
during the scattering process, and therefore increase or decrease in wavelength respectively.
If the molecule is promoted from a ground to a virtual state and then drops back down to a
(higher energy) vibrational state then the scattered photon has less energy than the incident
photon, and therefore a longer wavelength. This is called Stokes scattering. If the molecule is
in a vibrational state to begin with and after scattering is in its ground state then the scattered
photon has more energy, and therefore a shorter wavelength. This is called anti-Stokes
scattering.
Three different forms of scattering

Only about 1 in 107 photons undergo Stokes Raman scattering and so this is usually swamped
by the far more prominent Rayleigh scattering. The amount of anti-Stokes scattering is even
less than this. The difference in intensity of the Stokes and anti-Stokes components is due to
the different number of molecules in each state initially. The population follows the
Boltzmann distribution:  N ∝exp (−E/k B T )

Therefore, there are exponentially fewer molecules that start out in the higher energy
vibrational state. Since it is these that give rise to the anti-Stokes scattering, this is much less
intense.

The disparity depends on the spacing of the energy levels. So, for the less widely spaced
rotational levels, the Stokes and anti-Stokes scattering are of similar magnitude. For the
vibrational levels, which are spaced further apart, the anti-Stokes signal is significantly
weaker than the Stokes signal.

The disparity is also reduced with increased temperature, and the difference can be used as a
measure of temperature.

The shift due to the Raman effect is determined by the spacing between the vibrational
states and the ground states i.e., by the phonons of the system. The Stokes and anti-Stokes
scattered light will be shifted an equal distance on opposite sides of the Rayleigh scattered
light. Therefore, the spectrum is symmetrical about the wavelength of light used, apart from
the difference in intensities.

Vibrational states

The frequencies of a molecule’s vibrational modes, and hence the shifts in wavenumber, are
determined by the reduced mass μ and the bond strength k.

As a simple example N2 has only one vibrational mode. The reduced mass is given by:

μ=m1 m 2 (m 1+ m2 )=14 u ×14 u (14 u+14 u)=7 u=1.162 ×10−26 kg

The two nitrogen atoms are joined by a strong triple bond, with a force constant k = 22.95 N
cm-1. The vibrations are simple harmonic, so the frequency, and hence wavenumber, can be
determined:

In this example the wavenumber is 235900 m-1 or 2359 cm-1.

Normally in Raman spectroscopy only the Stokes half of the spectrum is used, due to its
greater intensity.

In one of Raman’s experiments demonstrating inelastic scattering, he used light from the Sun
focused using a telescope to obtain a high intensity light. This was passed through a
monochromatic filter, and then through a variety of liquids where it underwent scattering.
After passing through these he observed it with a crossed filter that blocked the
monochromatic light. Some light was seen passing through this filter, which showed that its
wavelength had been changed.
Comparison with other types of spectroscopies

It is instructive to compare the process of Raman scattering with some other spectroscopic
techniques. In the commonly used infrared absorption spectroscopy, infrared light excites
certain vibrational frequencies of molecules and is absorbed by them, not re-emitted. This
gives an absorption spectrum, with bands at characteristic wavenumbers. Other absorption
techniques use higher energy radiation (e.g., ultraviolet) and raise electrons to an excited
state.

Fluorescence occurs when light (often UV) is incident on a molecule and promotes an
electron to an excited state. The molecule is also vibrating. Firstly, it relaxes from its
vibrational state, dissipating this energy (normally as heat). Then when it drops back down to
the ground state, the photon released has less energy than the incident photon. The increased
wavelength often means that the light is now in the visible region. This is how fluorescent
lighting works, by ionisation of mercury to produce UV light, which is then absorbed by a
fluorescent coating and re-radiated as visible light. Fluorescence can also be used for
spectroscopy.

Raman active modes

The Raman shift depends on the energy spacing of the molecules’ modes. However not all
modes are “Raman active” i.e., not all appear in Raman spectra. For a mode to be Raman
 dα
active it must involve a change in the polarizability, α of the molecule i.e.  ( ) ≠ 0 where q
dq e
is the normal coordinate and e the equilibrium position.

When a molecule is in an electric field, its distribution of charge is displaced. This induces a
dipole μ. The polarizability α relates this dipole to the electric field:

μ=αE

As a simple rule of thumb, the polarizability is proportional to the volume occupied by the
molecule.

The polarizability may be anisotropic. It can be represented by a polarizability ellipsoid,

which is a 3D surface. The distance of a point (i) on the surface from the molecule’s electrical
centre is inversely proportional to the square root of the polarizability along the line from that
point to the centre.

r i ∝1/α i

This is known as spectroscopic selection. Some vibrational modes (phonons) can cause this.
These are generally the most important, although electronic modes can have an effect, and
rotational modes may be observed in gases at low pressure.

The spectroscopic selection rule for infrared spectroscopy is that only transitions that cause a
change in dipole moment can be observed. Because this relates to different vibrational
transitions than in Raman spectroscopy, the two techniques are complementary. In fact, for
centrosymmetric (centre of symmetry) molecules the Raman active modes are IR inactive,
and vice versa. This is called the rule of mutual exclusion.

The origin of Stokes and anti-Stokes scattering due to vibrational modes can be explained in
terms of the oscillations involved. The polarisability (α) of the molecule depends on the bond
length, with shorter bonds being harder to polarise than longer bonds. Therefore, if the
polarisability is changing then it will oscillate at the same frequency that the molecule is
vibrating (νvib).

Polarisability of the molecule:

α=α0+α1 sin(2πνvibt)

There is an external oscillating electric field from the photon, with a frequency νp:

E =  E0 sin (2 π  νp t)

Therefore, the induced dipole moment is:    

pind = αE=(α0+α1sin(2πνvibt)) ×E0sin(2πυpt)

Using the trigonometric identity:

sinA × sinB=(cos ( A−B)−cos( A+ B))/2

The induced dipole moment is:

pind=α0E0sin(2πυpt) +α0E02cos(2π(υp−νvib) t) −α0E02cos(2π(υp+νvib) t)

A dipole moment oscillating at frequency ν results in a photon of frequency ν. Therefore, in

this case there are photons scattered at frequency νp (Rayleigh scattering), νp – νvib (Stokes

scattering) and νp + νvib (anti-Stokes scattering).

Of course, if the polarisability is not changing then the dipole moment will simply oscillate at
frequency νp, and only Rayleigh scattering will occur. This is the origin of the spectroscopic
selection rule for Raman scattering.

The Raman (and IR) activity of more complicated molecules can be determined using their
symmetry and group theory.

The above is based on single molecules in a gas, and hence not interacting with neighbours.
In materials science Raman techniques are more often used for solids, where molecules
cannot be taken individually. In crystalline materials vibrations are quantised as phonons,
modes determined by the crystal structure. The spectroscopic selection rule still applies, i.e.
only phonons with a change in polarisability are Raman active. Phonons are generally of a
lower frequency than the vibrations in gases, so result in lower wavenumber shifts. Structural
information can therefore be determined from these shifts.
Crystal orientation can also be determined from the polarization of the scattered light.

Method (dispersive Raman spectroscopy)

Raman used light from the Sun focused through a telescope to achieve a high enough
intensity in his scattered signal. Modern spectrometers use both improved sources and more
sensitive detectors to obtain better results. Early spectrometers used mercury arc lamps as a
light source. Now lasers are normally employed due to their high intensity, single wavelength
and coherent beam.

Initial spectrometers used photographic plates to detect the light. The advent of more
sensitive photomultiplier tubes led to their widespread use, allowing the data to be collected
and manipulated electronically. However, they had the disadvantage of only being able to
count one wavelength at a time. Modern spectrometers use charge-coupled devices (CCDs)
that combine the advantages of the previous techniques, being highly sensitive, electronic,
and able to measure a whole spectrum at once.

A charge-coupled device (CCD) is an integrated circuit containing an array of linked, or

coupled, capacitors. Under the control of an external circuit, each capacitor can transfer
its electric charge to a neighbouring capacitor. CCD sensors are a major technology used
in digital imaging.
In a CCD image sensor, pixels are represented by p doped metal oxide
semiconductor (MOS) capacitors. These MOS capacitors, the basic building blocks of a
CCD, are biased above the threshold for inversion when image acquisition begins, allowing
the conversion of incoming photons into electron charges at the semiconductor-oxide
interface; the CCD is then used to read out these charges. Although CCDs are not the only
technology to allow for light detection, CCD image sensors are widely used in professional,
medical, and scientific applications where high-quality image data are required. In
applications with less exacting quality demands, such as consumer and professional digital
cameras, active pixel sensors, also known as CMOS sensors.

The chief difficulty in Raman spectroscopy is preventing overlapping of the Raman signal by
stray light from the far more intense Rayleigh scattering. Interference notch filters are
commonly used, which filter out wavelengths within approximately 100 cm-1 of the laser
wavelength. However, these are obviously of no use for studying low Raman shifts (e.g.,
those produced by low frequency phonons) within this region. One improvement is to use
multiple stages for dispersion, with either double or triple spectrometers. Holographic
diffraction gratings can be used which result in much less stray light than ruled ones.

Ruled gratings are made by etching a surface mechanically with a cutting tip, usually
diamond. Holographic diffraction gratings are formed by introducing an interference pattern
onto a layer of photosensitive material. The material is then treated with chemicals that only
dissolve it where the light interfered constructively.
An important consideration in Raman spectroscopy is the spectral resolution, the ability to
resolve features within the spectrum. There are two ways to increase spectral resolution, by
increasing the focal length or by changing the grating used to disperse the spectrum.
Doubling the focal length approximately doubles the spectral resolution. Similarly doubling
the density of lines on the grating results in twice the dispersion and twice the spectral
resolution. However higher density gratings have restricted working ranges e.g., a grating
with 2000 lines per mm cannot be used for infrared work.

The choice of wavelength used is important, and can range from the near infrared into the
ultraviolet. As already mentioned, the choice may be limited by the density of the diffraction
grating. In addition, for materials that show fluorescence it is vital to choose a longer
wavelength that will minimise fluorescence, as otherwise this will swamp the weak Raman
effect. However, higher energy ultraviolet lasers can be useful for penetrating certain samples
where fluorescence is not a problem. Another consideration is that visible lasers are generally
easier to work with. These varying factors mean that many spectrometers have a number of
lasers, which can be switched as appropriate. Of course, different lasers will require different
filters to remove the Rayleigh scattered light.

Raman micro spectroscopy

Raman spectroscopy can also be used for microscopic analysis and imaging. There are two
main methods: direct imaging and hyperspectral imaging (chemical imaging).

Direct imaging involves examining the whole sample for characteristic shifts e.g., of a single
compound. This generates an image showing the distribution of that compound.

In hyperspectral imaging Raman spectra are taken at points across the sample, so that
multiple compounds and their distributions can be identified. The disadvantage is that with a
spectrum taken for every pixel, this requires a lot of computing power and storage space.

Alternative techniques

Fourier transform (FT) Raman

Unlike dispersive Raman spectroscopy, which obtains a spectrum by diffraction of the
different wavelengths, Fourier transform (FT) Raman creates an interference pattern that can
be analysed to recover the spectrum. It has the advantage of being faster than the dispersive
technique, but is limited in resolution and choice of laser wavelength.

Stimulated Raman

Stimulated Raman scattering is a non-linear phenomenon that results in a much larger Raman
signal than standard scattering (4 to 5 orders of magnitude greater). It can be triggered with a
strong laser pulse. Only the strongest Raman active mode is excited at first, but scattering
from it can be strong enough to excite the second mode, which in turn can excite the third and
so on in a cascade effect.

Resonance Raman

Another effect that greatly increases the magnitude of scattering is Resonance Raman (RR).
This occurs when the energy of the incident radiation is close to that of an electronic
excitation energy (i.e., the band gap). Tuneable lasers can be used to achieve this. The Raman
scattering of vibrational modes around this excited state is then greatly enhanced by
resonance effects.

Surface Enhanced Raman Spectroscopy (SERS)

Surface Enhanced Raman Scattering (SERS) is a process that can occur when samples are
adsorbed on gold or silver surfaces. It results in a vast increase in the Raman effect, and is
therefore useful for spectroscopy. Though the mechanism is not very well understood, it is
believed to be a combination of chemical enhancement of polarisability by bonds formed
between the sample and the surface, and electromagnetic resonance of small gold or silver
particles. This effect can be combined with Resonance Raman for Surface Enhanced
Resonance Raman Spectroscopy (SERRS), which results in very strongly enhanced signals,
up to 1014 times more intense than standard Raman scattering.

Coherent Anti-Stokes Raman Spectroscopy (CARS)

Coherent Anti-Stokes Raman Spectroscopy (CARS) is a technique involving two lasers. One
is of a fixed frequency ν1 and the other is tuneable to a lower frequency ν2. When combined
they result in coherent radiation at frequency

ν' = 2 ν1 - ν2

along with a number of other frequencies.

If there is a Raman active mode with characteristic frequency νm, then when the second laser
is tuned such that

ν2 = ν1 - νm

then the coherent emission emerges in a high intensity narrow beam with frequency

ν' = 2 ν1 - (ν1 - νm) = ν1 + νm

This is the anti-Stokes frequency, hence the name.

Raman optical activity – compares polarisations

Raman optical activity is a technique which compares the different polarisations of Raman
scattered light from chiral molecules such as those found in biology, in order to determine
more about their structure. This can also be combined with amplifying techniques such as
resonance and surface enhancement.

Advantages and disadvantages

Advantages...

Raman spectroscopy has a number of advantages over other analysis techniques.

 Can be used with solids, liquids or gases.

 No sample preparation needed. For infrared spectroscopy solids must be ground into
KBr pellets or with nujol to form a mull.

 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 down fibre optic cables for remote sampling.

...and 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.

 Can be swamped by fluorescence from some materials.

Applications

There are a huge number of applications of Raman spectroscopy. Below are a few notable
examples.
Measuring/mapping stress

Raman spectroscopy can be used to measure stress and strain in materials. Tensile strain
increases the length of the bonds and the tension in them, hence changing the frequency
of the phonons. It therefore causes a shift in the observed Raman bands towards lower
wavenumbers.

Forensics, explosives /drugs detection

Advances in technology have led to much smaller spectrometers, which are moving from
the laboratory bench towards handheld devices that can be used for analysis in the field.
They may be linked to a library of spectra, and can be used by law enforcement and
customs officials to detect explosives, drugs and other chemicals. They are also useful for
quickly identifying possibly hazardous materials e.g., after a spillage.
Pictured is a Raman integrated tuneable sensor (RAMITS) developed by the US
government. It has a probe coated with silver nanoparticles, which allow Surface
Enhanced Raman Spectroscopy, boosting the signal. The instrument is handheld and
battery powered.

Process monitoring

Raman spectroscopy is a non-destructive process, and can be used to monitor industrial

processes. The speed of analysis means that it can give almost real-time information.
Another advantage is that the light to be monitored can be sent down fibre-optics, so that
the Raman equipment can be located some distance away from the actual processing.

Uncovering artistic techniques

As well as monitoring state of the art processes, Raman spectroscopy is being used to
uncover the secrets of ancient artefacts. Scientists at Trinity College in Dublin are using
Raman spectroscopy to examine the famous Book of Kells, an illustrated manuscript
dating from the 9th century. They hope to determine the composition and origins of the
paper, inks and pigments used, which will tell them about techniques used and trade
routes of the age.
Life on Mars

Raman spectroscopy could also be used to search for life on Mars. Modern Raman
technology has been miniaturised to the point that a small spectroscope will be carried on
a future mission to the planet. The instrument will be used to look for evidence of life
and/or life supporting conditions either in the present or the distant past, as well as more
general analysis of the Martian surface. Similar instruments could be featured on missions
to other potential sites of life such as Europa or Calisto.

Carbon nanotubes

Because of their structure, carbon nanotubes can be made to resonate with light. They
may resonate with either the incident wavelength, or Raman scattered wavelengths.
Resonance can also occur for a number of different modes. Some of the most important
are the radial breathing mode, the disorder mode and the high energy mode.

Observations of these can be used to determine important properties of the nanotubes,

such as their diameter and strain. Raman spectroscopy is one of the easiest ways of
measuring these vital properties.