Raman Spectroscopy

Raman spectroscopy (named after Sir C. V. Raman) is a spectroscopic technique used to

observe vibrational, rotational, and other low-frequency modes in a system. It relies on
inelastic scattering, or Raman scattering, of monochromatic light, usually from a laser in
the visible, near infrared, or near ultraviolet range. The laser light interacts with
molecular vibrations, phonons or other excitations in the system, resulting in the energy
of the laser photons being shifted up or down. The shift in energy gives information about
the vibrational modes in the system. Infrared spectroscopy yields similar, but
complementary, information.
Typically, a sample is illuminated with a laser beam. Light from the illuminated spot is
collected with a lens and sent through a monochromator. Wavelengths close to the laser
line due to elastic Rayleigh scattering are filtered out while the rest of the collected light
is dispersed onto a detector.
Spontaneous Raman scattering is typically very weak, and as a result the main difficulty
of Raman spectroscopy is separating the weak inelastically scattered light from the
intense Rayleigh scattered laser light. Historically, Raman spectrometers used
holographic gratings and multiple dispersion stages to achieve a high degree of laser
rejection. In the past, photomultipliers were the detectors of choice for dispersive Raman
setups, which resulted in long acquisition times. However, modern instrumentation
almost universally employs notch or edge filters for laser rejection and spectrographs
(either axial transmissive (AT), Czerny-Turner (CT) monochromator, or FT (Fourier
transform spectroscopy based), and CCD detectors.
There are a number of advanced types of Raman spectroscopy, including surfaceenhanced Raman, resonance Raman, tip-enhanced Raman, polarised Raman, stimulated
Raman (analogous to stimulated emission), transmission Raman, spatially offset Raman,
and hyper Raman.

Energy level diagram showing the states involved in Raman signal. The line thickness is
roughly proportional to the signal strength from the different transitions.
Theory
The Raman effect occurs when light impinges upon a molecule and interacts with the
electron cloud and the bonds of that molecule. For the spontaneous Raman effect, which
is a form of light scattering, a photon excites the molecule from the ground state to a
virtual energy state. When the molecule relaxes it emits a photon and it returns to a
different rotational or vibrational state. The difference in energy between the original
state and this new state leads to a shift in the emitted photon's frequency away from the
excitation wavelength. The Raman effect, which is a light scattering phenomenon, should
not be confused with absorption (as with fluorescence) where the molecule is excited to a
discrete (not virtual) energy level.
If the final vibrational state of the molecule is more energetic than the initial state, then
the emitted photon will be shifted to a lower frequency in order for the total energy of the
system to remain balanced. This shift in frequency is designated as a Stokes shift. If the
final vibrational state is less energetic than the initial state, then the emitted photon will
be shifted to a higher frequency, and this is designated as an anti-Stokes shift. Raman
scattering is an example of inelastic scattering because of the energy transfer between the
photons and the molecules during their interaction.
A change in the molecular polarization potential or amount of deformation of the
electron cloud with respect to the vibrational coordinate is required for a molecule to
exhibit a Raman effect. The amount of the polarizability change will determine the
Raman scattering intensity. The pattern of shifted frequencies is determined by the
rotational and vibrational states of the sample. This dependence on the polarizability
differs from Infrared spectroscopy where the interaction between the molecule and light
is determined by the dipole moment; this contrasting feature allows to analyze transitions
that might not be IR active via Raman spectroscopy, as exemplified by the rule of mutual
exclusion in centrosymmetric molecules.
The adventages of Raman spectroscopy
Whether the goal is qualitative or quantitative data, Raman analysis is one of the few
technique which can provide key information, easily and quickly, detailing the chemical
composition and the structure of the investigated materials. Localized or extended
(mapping) investigations can be done under microscope by using micro-Raman (Raman
micro-probe, Raman laser micro-probe) and, more recently, by using NanoRamanTM.
Raman spectroscopy is :

Non destructive

Non invasive

No need of sample preparation

Information rich

Need only some milligram (or picogram) of material (gas, liquid or solid)

Raman spectrometers detect also spin waves (magnons) in semi-magnetic crystals. As

for phonons, spin waves with small wave number (near zero, that means at the centrum of
the Brillouin zone) are only detected.
Get the full picture of the sample properties

Chemical composition & component identification

Molecular structure characterisation

Phase transition monitoring

Components distribution at micron & sub-micron scale

Stress measurements

Hyperspectral imaging

Reaction monitoring

High thoughput screening

At last, measurements were done usually at room temperature. Nevertheless, they can
be done at low or high temperature by using appopriate cells (cryostat or furnace with
glass or quartz window(s)).They also can be done under hydrostatic or uniaxial pressure
by using diamond anvil cells. Such equipments were very convenient to simulate
geological condition under the earth's crust.