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.
Superparamagnetic nanoparticles
• 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.
12
