Interpretation of Vibrational Spectra

Qualitative Method
A simple way to qualitatively interpret vibrational spectra is the ‘‘fingerprint’’
method of identifying materials.

The fingerprint method includes spectrum comparison with a reference, and

identification of characteristic bands in spectra

Spectrum Comparison

A sample can be identified if its spectrum matches a reference in both band

positions and intensities in the whole spectrum range

Comparison of sample and reference spectra should satisfy the following

conditions; otherwise the spectra are not comparable:
• both sample and reference spectra must be in the same physical state (for
example, either both are liquid or solid) and
• both sample and reference must be measured using the same techniques (for
example, both are dispersed with KBr for FTIR measurement)
Typical applications of spectrum comparison include verifying whether synthetic
materials are identical to their natural counterparts, and determining the stability of
materials over a period of time or in certain environments

For spectrum comparison, a region of spectrum below 1200 cm−1 is of importance,

often called the ‘‘fingerprint region.’’

Figure: Comparison of Raman spectra of AHMo5O16(H2O)H2Om: A = (1) NH4+;

(2) K+; (3) Na+; and (4) compound spectrum in aqueous solutions.
Identifying Characteristic Bands
Vibrational frequencies of some atom groups are quite independent even if they
are parts of larger molecules and crystals. Such vibration bands serve as
characteristic bands for atom groups.

A characteristic band for an atom group should satisfy the following conditions:
• the band occurs in all spectra of materials containing the atom group and
• the band is absent when materials do not contain the atom group

Classical mechanics shows the vibrational frequency relationship

Vibrational frequency increases with the bond strength and decreases with atomic
mass.
Characteristic bands in Figure show ranges instead of exact wave numbers.
This phenomenon reflects the fact that the vibrational frequencies also depend on
neighboring atoms in materials, even though the frequencies are mainly determined
by bond strength and atomic masses.

Figure: Positions of characteristic bands in vibrational spectra for some

diatomic stretching vibrations.
Band Intensities
Interpreting the intensities of vibrational bands in a vibrational spectrum is not
straightforward. The band intensity is not simply proportional to the number of
atoms involved with such specific vibration. The intensity varies with types of bonds
and types of spectroscopy, either IR or Raman.

The intensity of an IR absorption band is proportional to the square of its change in

dipole moment during vibration.

The intensity of a Raman shift is proportional to the square of its change in

polarizability during vibration

In practice, some simple rules are useful to estimate the band intensities:
• polar bonds yield intense IR but weak Raman bands;
• weak polar or nonpolar bonds yield intense Raman but weak IR bands; and
• intensity increases with number of identical structural elements in a
molecule
Quantitative Methods

Quantitative Analysis of Infrared Spectra

The concentration of certain components in a multicomponent sample can be

determined by quantitative analysis from the intensities of its vibration bands.

For an IR spectrum concentration is proportional to absorbance (A) according to the

absorption law, also called Beer’s Law

The concentration (C) can be determined by measuring the magnitude of

absorbance from an IR spectrum, if a and l are known.

The absorbance A is commonly obtained by peak-height measurement in quantitative

IR analysis.
 Figure 9.45 Baseline method for determining absorbance.

For analysis of two-component materials, a ratio method can be used for

quantitative analysis based on Beer’s Law.

The ratio of their absorbance The path lengths should be the same in the
will be calculated same sample. We can determine the
ratio
For analysis of multicomponent materials with overlapping vibration bands,
Beer’s Law can still be used because absorbances of components are additive.
Combining a and l as a single parameter k, the absorbance of components is
expressed.

A three-component system should have the following expressions.

The concentrations of components should be resolved as C

where P = K−1, the inverse of K matrix.

Quantitative Analysis of Raman Spectra

Raman spectroscopy is a scattering, not an absorption technique as FTIR. Thus, the

ratio method cannot be used to determine the amount of light scattered unless an
internal standard method is adopted.
The internal standard method requires adding a known amount of a known component to each
unknown sample.