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The document discusses several types of Raman spectroscopy techniques: Classic back-scattering Raman spectroscopy measures plasma density using the wavelength of backscattered radiation. Raman backscattering can estimate laser intensity and optimal plasma density. Transmission Raman spectroscopy analyzes opaque/turbid materials by collecting Raman signals transmitted through the sample. It is used to understand API concentration, content uniformity, polymorphism, crystallinity, and powder composition/purity. Surface-enhanced Raman spectroscopy (SERS) enhances weak Raman signals using metallic nanostructures. SERS provides high chemical selectivity like Raman spectroscopy but signal may come from only part of a molecule. Reproducibility of SERS substrates is still a major issue limiting its use

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63 views

622 Assignment

The document discusses several types of Raman spectroscopy techniques: Classic back-scattering Raman spectroscopy measures plasma density using the wavelength of backscattered radiation. Raman backscattering can estimate laser intensity and optimal plasma density. Transmission Raman spectroscopy analyzes opaque/turbid materials by collecting Raman signals transmitted through the sample. It is used to understand API concentration, content uniformity, polymorphism, crystallinity, and powder composition/purity. Surface-enhanced Raman spectroscopy (SERS) enhances weak Raman signals using metallic nanostructures. SERS provides high chemical selectivity like Raman spectroscopy but signal may come from only part of a molecule. Reproducibility of SERS substrates is still a major issue limiting its use

Uploaded by

lebogang
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© © All Rights Reserved
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Download as DOCX, PDF, TXT or read online on Scribd
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Question 2

Classic back-scattering Raman Spectroscopy


The stimulated Raman scattering instability in plasmas occurs when an incident pump laser
pulse scatters from an electron plasma wave. The resulting scattered electromagnetic waves are
downshifted (Stokes) and upshifted (anti-Stokes) by the plasma frequency. For direct
backscattering, the growth rate is maximized, and the ponderomotive force resulting from the
beating of the Stokes and pump waves reinforce the plasma wave. This, in turn, increases the
energy scattered into the Stokes sideband. The feedback process continues until the Stokes
wave itself becomes unstable or another nonlinear process takes over. Amplification of the
Raman backscattered wave is physically equivalent to one of the operating regimes of the free
electron laser. In either case, relativistic analysis of the scattering process shows that the
frequency is a complex-valued number with both real and imaginary parts. The imaginary part
is of course connected with growth of the backscattered wave. The real part results in a pump
amplitude dependent frequency shift that is physically distinct from the shift associated with
the effective electron mass increase due to relativity.

The wavelength of the back scattered radiation is commonly used to measure the plasma
density in gas jets and plasma channels used in laser wakefield acceleration (LWFA)
experiments. Raman backscattered radiation can be used to estimate the laser intensity inside
a known density plasma target, provide information on the self-focusing conditions, or
determine the optimal plasma density for quasi-linear wakefield acceleration. Raman
backscattering (RBS) is limited to intermediate laser intensities, below those achievable by
modern ultra-intense lasers.

Transmission Raman
Transmission Raman spectroscopy (or TRS) is a form of Raman analysis which is ideally suited
for bulk analysis of opaque/turbid materials. Transmission Raman is based on the collection
of Raman light propagating through the sample in the direction of the excitation laser – in
essence, the sample is illuminated with the excitation laser from one side, and the Raman signal
is collected from the other. Despite the sample being opaque light from the laser can pass
through the sample via light scattering processes.
Transmission Raman spectroscopy can be used to understand:

 API concentration
 Content uniformity
 Polymorphism
 Crystallinity
 Powder composition and purity
 Solid form
It is limited to translucent samples.
Surface-Enhanced Raman Spectroscopy
 Surface-enhanced Raman spectroscopy (SERS) is one of the answers to low Raman
signals. The obvious advantage of SERS is the enhancement of the signal, which
sometimes cannot even be measured by classical Raman spectroscopy because of the
low concentration of the analyte. SERS inherits, of course, the high chemical selectivity
of Raman spectroscopy. SERS spectra and Raman spectra are basically similar, but they
are not always the same. There are some reasons for that. The SERS effect is highly
localized, therefore, only a signal from part of the molecule, close to the substrate, will
be enhanced. When the molecule is adsorbed on the surface, its symmetry might slightly
change, and so do the selection rules. Also, because plasmon resonance is wavelength
dependent, the different spectral regions of the spectrum may be enhanced differently.

 SERS is for those who analyse very small amounts of materials or substances of low
Raman efficiency, which could be the case in applications related to pharmaceuticals,
life sciences, forensics, or art.

The limitations of SERS

 The reproducibility of the SERS supports is still the major issue, which probably
explains the number of publications related to substrate development.
 Other issues are the capacity of molecules to attach to the substrate and signal
enhancement.
 The holy grail — substrates that give high enhancement, are reproducible, uniform, and
easy and cheap to mass produce — has not been found yet. This is very well
summarized in the "SERS uncertainty principle": We either have high enhancement
and low reproducibility, essential for very low concentration measurements like single-
molecule SERS; or we have relatively good reproducibility with less impressive
enhancement, which is still a very interesting option in the case of routine analysis when
the classical Raman signal is not strong enough
Time Resolved Raman Spectroscopy

Resonance Raman Spectroscopy


 Resonance Raman scattering refers to a phenomenon in which Raman line intensities
are greatly enhanced by excitation with wavelengths that closely approach that of an
electronic absorption peak of an analyte. Under this circumstance, the magnitudes of
Raman peaks associated with the most symmetric vibrations are enhanced by a factor
of 102 to 106. Therefore, resonance Raman spectra have been obtained at analyte
concentrations as low as 10-8 M.
 The most important application of resonance Raman spectroscopy has been to the study of
biological molecules under physiologically significant conditions; that is, in the presence
of water and at low to moderate concentration levels. As an example, the technique has
been used to determine the oxidation state and spin of iron atoms in hemoglobin and
cytochrome-c.
 It was developed for the pharmaceutical industry. It requires diffusing materials, such as
pharmaceutical tablets, and provides information about the whole volume of the sample
without a strong influence on the tablet coating, which can be a problem in classical
backscattering configuration. It can be used for the analysis of component concentration,
and content uniformity. It also works for capsules and other materials outside of the
pharmaceutical field, which are diffusing, translucent, and require whole sample analysis.

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