Raman spectroscopy

Raman spectroscopy is an analytical technique where scattered light is used to measure the vibrational
energy modes of a sample. It is named after the Indian physicist C. V. Raman who, together with his
research partner K. S. Krishnan, was the first to observe Raman scattering in 1928.
- Raman spectroscopy can provide both chemical and structural information, as well as the
identification of substances through their characteristic Raman ‘fingerprint’. Raman spectroscopy
extracts this information through the detection of Raman scattering from the sample.

What is Raman Scattering?

When light is scattered by molecule, the oscillating electromagnetic field of a photon induces a
polarization of the molecular electron cloud which leaves the molecule in a higher energy state with
the energy of the photon transferred to the molecule. This can be considered as the formation of a
very short-lived complex between the photon and molecule which is commonly called the virtual state
of the molecule. The virtual state is not stable and the photon is re-emitted almost immediately, as
scattered light.
Rayleigh scattering
In the vast majority of scattering events, the energy of the molecule is unchanged after its interaction with the
photon; and the energy, and therefore the wavelength, of the scattered photon is equal to that of the incident
photon. This is called elastic (energy of scattering particle is conserved) or Rayleigh scattering and is the
dominant process.

In a much rarer event (approximately 1 in 10 million photons) Raman scattering occurs, which is an inelastic
scattering process with a transfer of energy between the molecule and scattered photon. If the molecule gains
energy from the photon during the scattering (excited to a higher vibrational level) then the scattered photon
loses energy and its wavelength increases which is called Stokes Raman scattering (after G. G. Stokes). Inversely,
if the molecule loses energy by relaxing to a lower vibrational level the scattered photon gains the
corresponding energy and its wavelength decreases; which is called Anti-Stokes Raman scattering. Quantum
mechanically Stokes and Anti-Stokes are equally likely processes. However, with an ensemble of molecules, the
majority of molecules will be in the ground vibrational level (Boltzmann distribution) and Stokes scatter is the
statistically more probable process.

Stokes Raman scatter is always more intense than the anti-Stokes and for this reason, it is nearly always the
Stokes Raman scatter that is measured in Raman spectroscopy.
Raman Shift
It is clear from the above, that the wavelength of the Raman scattered light will depend on the wavelength of
the excitation light. This makes the Raman scatter wavelength an impractical number for comparison
between spectra measured using different lasers. The Raman scatter position is therefore converted to a
Raman shift away from excitation wavelength:

The first term is the wavenumber Raman shift in cm-1, λ(0) is the wavelength of the excitation laser in nm,
and λ(1) is the wavelength of the Raman scatter in nm.
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 active it must involve a
change in the polarisability, α of the molecule.

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.
vibrating sample magnetometer
A vibrating sample magnetometer (VSM) is a scientific instrument that measures the magnetic properties of
ferromagnetic materials. VSMs are used to determine a material's magnetic susceptibility and the strength of the
magnetic field it produces. VSMs are useful in research and development, production testing, and quality control.
Here's how a VSM works to measure the magnetic properties of a ferromagnetic material:
1.The sample is placed in a constant magnetic field.
2.The sample is moved up and down at a set frequency.
3.The sample's magnetic dipole moves, creating an electric field.
4.The electric field induces a current in a set of pickup coils.
5.The current is proportional to the sample's magnetization.
6.A hysteresis curve is recorded, which can be used to deduce the sample's magnetic properties.
VSMs can be used to determine the following properties of ferromagnetic materials

Saturation magnetization, Remnant magnetization, Coercive fields, and Curie temperatures.

• It is observed that as the particle size decreases, a critical particle size reached where the grain can no longer accommodate a
domain wall.
• Below this critical size, the grain contains a single domain (SD). An SD grain is uniformly magnetized to its saturation
magnetization.
• If the particle size continues to decrease within the SD range, another critical threshold is reached, at which remanence and
coercivity go to zero. When this happens, the grain becomes Superparamagnetic.

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