Raman Spectroscopy

 Inelastic scattering means that the frequency of photons in monochromatic light changes upon interaction with a sample. Photons of the laser light are absorbed by the sample and then reemitted. Frequency of the reemitted photons is shifted up or down in comparison with original monochromatic frequency, which is called the Raman effect.This shift provides information about vibrational, rotational and other low frequency transitions in molecules. Raman spectroscopy can be used to study solid, liquid and gaseous samples.The Raman effect is based on molecular deformations in electric field E determined by molecular polarizability α. The laser beam can be  considered as an oscillating electromagnetic wave with electrical vector E. Upon interaction with the sample it induces electric dipole moment P = αE which deforms molecules. Because of periodical deformation, molecules start vibrating with characteristic frequency υm.

Amplitude of vibration is called a nuclear displacement. In other words, monochromatic laser light with frequency υ0 excites molecules and transforms them into oscillating dipoles. Such oscillating dipoles emit light of three different frequencies  when:
1. A molecule with no Raman-active modes absorbs a photon with the frequency υ0. The excited molecule returns back to the same basic vibrational state and emits light with the same frequency υ0 as an excitation source. This type if interaction is called an elastic Rayleigh scattering.
2. A photon with frequency υ0 is absorbed by Raman-active molecule which at the time of interaction is in the basic vibrational state. Part of the photon’s energy is transferred to the Raman-active mode with frequency υm and the resulting  frequency of scattered light is reduced to υ0
– υm. This Raman frequency is called Stokes frequency, or just “Stokes”.
3. A photon with frequency υ0 is absorbed by a Raman-active molecule, which, at the time of interaction, is already in the excited vibrational state. Excessive energy of excited Ramanactive mode is released, molecule returns to the basic vibrational state and the resulting frequency of scattered light goes up to υ0 + υm. This Raman frequency is called AntiStokes frequency, or just “Anti-Stokes”

About 99.999% of all incident photons in spontaneous Raman undergo elastic Rayleigh scattering. This type of signal is useless for practical purposes of molecular characterization. Only about 0.001% of the incident light produces inelastic Raman signal with frequencies υ0 ± υm. Spontaneous Raman scattering is very weak and special measures should be taken to distinguish it from the predominant Rayleigh scattering. Instruments such as notch filters, tunable filters, laser stop apertures, double and triple spectrometric systems are used to reduce Rayleigh scattering and obtain high-quality Raman spectra.

2. Instrumentation 

                                                                                                                                                                              From sas.upenn

A Raman system typically consists of four major components:
1. Excitation source (Laser).
2. Sample illumination system and light collection optics.
3. Wavelength selector (Filter or Spectrophotometer).
4. Detector (Photodiode array, CCD or PMT).
A sample is normally illuminated with a laser beam in the ultraviolet (UV), visible (Vis) or near infrared (NIR) range. Scattered light is collected with a lens and is sent through interference filter or spectrophotometer to obtain Raman spectrum of a sample.Since spontaneous Raman scattering is very weak the main difficulty of Raman spectroscopy is separating it from the intense Rayleigh scattering. More precisely, the major problem here is not the Rayleigh scattering itself, but the fact that the intensity of stray light from the Rayleigh scattering may greatly exceed the intensity of the useful Raman signal in the close proximity to the laser wavelength. In many cases the problem is resolved by simply cutting off the spectral range close to the laser line where the stray light has the most prominent effect. People use commercially available interference
(notch) filters which cut-off spectral range of ± 80-120 cm-1 from the laser line. This method is efficient in stray light elimination but it does not allow detection of low-frequency Raman modes in the range below 100 cm-1.
Stray light is generated in the spectrometer mainly upon light dispersion on gratings and strongly depends on grating quality.Raman  spectrometers typically use holographic gratings which normally have much less manufacturing defects in their structure then the ruled once. Stray light produced by holographic gratings is about an order of magnitude less intense then from ruled gratings of the same groove density.
Using multiple dispersion stages is another way of stray light reduction. Double and triple spectrometers allow taking Raman spectra without use of notch filters. In such systems Raman-active modes with frequencies as low as 3-5 cm-1  can be efficiently detected.In earlier times people primarily used single-point detectors such as photon-counting Photomultiplier Tubes (PMT). However, a single Raman spectrum obtained with a PMT detector in wavenumber scanning mode was taking substantial period of time,slowing down any research or industrial activity based on Raman analytical technique. Nowadays, more and more often researchers use multi-channel detectors like Photodiode Arrays (PDA) or, more commonly, a Charge-Coupled Devices (CCD) to detect the Raman scattered light. Sensitivity and  performance of modern CCD detectors are rapidly improving. In many cases CCD is becoming the detector of choice for Raman spectroscopy.

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