Last Updated: April 2021

Version: 5
Understanding Raman Spectroscopy
Principles and Theory
Basic Raman Instrumentation

Figure 1

Raman Theory
Raman scattering is a spectroscopic technique that is complementary to infrared absorption spectroscopy.
The technique involves shining a monochromatic light source (i.e. laser) on a sample and detecting the
scattered light. Above is a simple schematic of a Raman spectrometer (Figure1).

The majority of the scattered light will pass through the sample without interaction. The result is the detector
will receive energy that is of the same frequency as the excitation source; this is known as Rayleigh or elastic
scattering. A very small amount of the scattered light (~ 1 in 107) is shifted in energy from the laser frequency.
This shift is known as a Raman or Stokes shift. At room temperature, the anti-Stokes-shifted Raman energy is
weaker than the Stokes-shifted energy-thus they are usually ignored and removed by filters. This due to
interactions between the incident electromagnetic waves and the vibrational energy levels of the molecules in
the sample. In other words, the interaction can be viewed as a perturbation of the molecule’s electric field.
Viewed at the molecular energy level (Figure 2), the Rayleigh scattering (no interaction) and the Stokes shift
(interaction) are energy difference between the incident and scattered photons is represented by the arrows of
different lengths.

Figure 2

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Vibrational Raman spectroscopy is not limited to intramolecular vibrations. Crystal lattice vibrations and other
motions of extended solids are Raman-active. Their spectra are important in such fields as geochemistry and
mineralogy. For Raman selection rules it can simply explained by electromagnetic field interactions within the
molecule’s bonds. The dipole moment, P. induced in a molecule by an external electric field, E, is proportional
to the field as shown in Equation 1.

P=E
Equation 1

The proportionality constant  is the polarizability of the molecule. The polarizability measures the ease with
which the electron cloud around a molecule can be distorted. The induced dipole emits or scatters light at the
optical frequency of the incident light wave. The change in the polarizability within the bond gives rise to
Raman scattering. Scattering intensity is proportional to the square of the induced dipole moment.

If a vibration does not greatly change the polarizability, then the polarizability derivative will be near zero, and
the intensity of the Raman band will be low. The vibrations of a highly polar moiety, such as the O-H bond, are
usually weak. An external electric field cannot induce a large change in the dipole moment and stretching or
bending the bond does not change, giving weak or not Raman signal. Typical strong Raman scatterers are
moieties with distributed electron clouds, such as carbon-carbon double bonds. The pi-electron cloud of the
double bond is easily distorted in an external electric field. Bending or stretching the bond changes the
distribution of electron density substantially and causes a large change in induced dipole moment.

Figure 3

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For polarizable molecules, the incident photon energy can excite vibrational modes of the molecules, yielding
scattered photons which are diminished in energy by the amount of the vibrational transition energies giving
rise to the peaks in a Raman spectrum. The number of peaks is related to the number of degrees of freedom a
molecule contains (Figure 3).

To be Raman active a molecule must have a change in its polarizability. Polarizability is a difficult concept to
visualize. The easiest way to describe it is as the relative tendency of the electron cloud to be distorted from its
normal shape.

Visual Explanation:

Figure 4

Figure 5

A Raman spectrum (Figure 6) is defined by plotting the intensity of this “shifted” light versus frequency results
in a Raman spectrum of the sample. Generally, Raman spectra are plotted with respect to the laser frequency
such that the Rayleigh band lies at 0 cm-1. On this scale, the band positions will lie at frequencies that
correspond to the energy levels of different functional group vibrations. The Raman spectrum can thus be
interpreted similar to the infrared absorption spectrum.

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Figure 6

Advantages of Raman spectroscopy

1. Sample Preparation; Little to no sample preparation is required is most cases. The sample can be placed
into the holder position and a spectrum can be retrieved.
2. Water as a solvent; Water is a weak scatterer; thus, it can be used as a solvent for a ‘difficult sample’ - no
special accessories are required for measuring in a aqueous solutions.
3. No need for nitrogen purging of the optical bench; Water and carbon dioxide vapors are very weak
scattering species.
4. Cheap and sample holders; Inexpensive glass sample holders are ideal in most cases.
5. Cleaner Spectra; Raman spectra are "cleaner" than mid-IR spectra - Raman bands are narrower, and
overtone and combination bands are generally weak.
6. Wide range of molecules to investigate; The standard spectral range reaches well below 400 cm-1, making
the technique ideal for both organic and inorganic species.
7. Investigate weak IR bands; Raman spectroscopy can be used to measure bands of symmetric linkages which
are weak in an infrared spectrum such as C=C, C-S and S-S.

Disadvantages of Raman Spectroscopy

1. Due to the low Raman intensities the detector sensitivity is paramount

2. Instrumentation is more expensive than typical mid-range IR
3. Laser can destroy sections of the sample if the power setting is too high
4. Fluorescence caused by the laser is a major concern with some samples

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Abbreviated Raman Bond Correlation Chart

Wavenumber Range (cm–1) Group Intensity

100–210 Lattice vibrations Strong
150–430 Xmetal-O Strong
250–400 C-C aliphatic chain Strong
425–550 S-S Strong
460–550 Si-O-Si Strong
490–660 C-I Strong
505–700 C-Br Strong
550–790 C-Cl Strong
580–680 C=S Strong
630–1250 C-C aliphatic chains Moderate
670–780 C-S Strong
720–800 C-F Strong
990–1100 Aromatic rings Strong
1020–1225 C=S Strong
1050–1210 Sulfonamide Moderate
1315–1435 Carboxylate salt Moderate
1320–1350 Nitro Very strong
1365–1450 Aromatic azo Very strong
1450–1505 Aromatic ring Moderate
1550–1610 Aromatic/hetero ring Strong
1550–1700 Amide Strong
1600–1710 Ketone Moderate
1610–1740 Carboxylic acid Moderate
1625–1680 C=C Very strong
1630–1665 C=N Very strong
1690–1720 Urethane Moderate
1710–1725 Aldehyde Moderate
1710–1745 Ester Moderate
1730–1750 Aliphatic ester Moderate
1735–1790 Lactone Moderate
1740–1830 Anhydride Moderate
1745–1780 Acid chloride Moderate
2020–2100 Isothiocyanate Moderate
2070–2250 Alkyne Strong
2220–2260 Nitrile Moderate
2530–2610 Th iol Strong
2770–2830 CH2 Strong
2810–2960 C-CH3 Strong
2870–3100 Aromatic C-H Strong
2900–2940 CH2 Strong
2980–3020 CH=CH Strong
3010–3080 =CH2 Strong
3150–3480 Amide Moderate
3150–3480 Amine Moderate

Contact the TRACES Manager for further details.

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