Raman Spectroscopy*)

Chotimah

*) McMohan, G., 2007: Analytical Instrumentation:

A Guide to Laboratory, Portable and Miniaturized Instruments, John Wiley & Sons Ltd, England.
 Introduction
 Infrared (IR) and Raman are vibrational spectroscopy techniques.
 They are extremely useful for providing structural information about molecules in terms of
their functional groups, the orientation of those groups and information on isomers.
 They can be used to examine most kinds of sample and are nondestructive.
 They can also be used to provide quantitative information.
 IR refers to the mid IR region, which covers the range 4000–400 cm-1 (2500–25,000 nm).
 Raman radiation spans the range 4000 down to about zero cm-1.
 IR and Raman spectroscopies are similar insofar as they both produce spectra because of
vibrational transitions within a molecule and use the same region of the electromagnetic
spectrum.
 They differ in how observation and measurement are achieved, since IR is an
absorption (transmission) method and Raman is a scattering method.
Some of the possible vibrations for a simple molecule upon absorption
of infrared radiation.
IR transmission spectrum of aspirin (The
transmission peaks at approximately 3000 cm -1
(broad band), 2900 cm -11 (sharp bands), 2600–
2700 cm -1 and 1700 cm -11 are due
to vibrations of the OH, aromatic CH, aliphatic
CH and the C"O bonds in the molecule
respectively.
The stretches in the region between 1500 cm -11
and 500 cm -11 are more diffi cult to
assign as this is the ‘fi ngerprint region’).

Raman spectrum of aspirin (with no sample

preparation required) (The Raman signals at
approximately 3100 cm -11 and 2900 cm -1 are due to
CH vibrations and the signal at 1700 cm -11 is due
to C"O vibrations in the molecule.
It can be seen by comparing this spectrum
to Figure 2.8 that the infrared and Raman spectra
are complementary to each other).
The infrared and Raman spectra of styrene/butadiene rubber illustrating the complementary nature of the two
techniques
(From ‘What is Raman Spectroscopy?’, Hendra, P., Int J Vib Spect, [www.ijvs.com] 1 (5), pp. 6–16 (1998)11.
Copyright John Wiley & Sons Limited. Reproduced with permission).
 Raman signals can be obscured by fluorescence so care must be taken when
choosing the energy source. Raman is primarily used as a non-contact quantitative
technique.
 Raman and IR are complementary techniques in that molecules that vibrate/rotate
in this region of the spectrum will generally give a spectrum in both.
 However, polar functional groups with low symmetry generally give strong IR
signals while molecules with polarizable functional groups with high symmetry
generally give strong Raman signals.
 Hence, strong infrared absorptions appear usually as weak Raman ones and vice
versa.
 Raman is not as sensitive to the environment of the molecule as IR.
 Also, Raman is relatively insensitive to water whereas the opposite is true of IR.
Schematic diagram of a
Michelson interferometer.

Schematic diagram of the inside of an FTIR

spectrometer showing the position
of the Michelson interferometer (Reproduced by kind
permission of Thermo Electron
Corp.).
Schematic diagram showing conversion of an interferogram to the required FTIR
spectrum
(Reproduced by kind permission of Thermo Electron Corp.).
Applications
 Infrared spectrometry can be used for testing emissions.
 For example, IR has been reported for determining carbon monoxide and
nitrogen oxide and other trace gases, remote sensing of volcanic gases and
trace analysis of halocarbons in the atmosphere, among many other
applications.
 IR is also employed in the beverage industry for monitoring alcohol, sugar
and water content in drinks, and sugars, fibres and acidity in juices.
 In the food industry, IR spectrometry is very useful for determining protein,
oil, ash, moisture and particle size in flour for following fermentation and
microbiological reactions and for the study of microorganisms in food
products.
 Raman spectrometry is often used for investigating biological samples
since water does not interfere signifi cantly, e.g. transformational changes
in proteins and lipids can be readily followed18.
 Raman spectrometry for inorganic compounds, especially metal
complexes, is also employed as it is a well understood area.
 Raman spectrometry is used extensively too in areas that are less well
known such as space research, deep ocean investigation and is a useful
technique in medical research and healthcare.