Unexpected bands other than Fundamental Frequencies :

Overtone and Combination Bands:

The sound we hear is a mixture of harmonics, that is, a fundamental frequency

mixed with multiples of that frequency. Overtone bands in an infrared spectrum
are analogous and are multiples of the fundamental absorption frequency. The
energy levels for overtones of infrared modes are illustrated in Figure 1.13. The
energy required for the first overtone is twice the fundamental, assuming evenly
spaced energy levels. Since the energy is proportional to the frequency absorbed
and this is proportional to the wavenumber, the first overtone will appear in the
spectrum at twice the wavenumber of the fundamental. Combination bands arise
when two fundamental bands absorbing at ν1 and ν2 absorb energy
simultaneously. The resulting band will appear at (ν1 + ν2) wavenumbers. SAQ 1.5
A molecule has strong fundamental bands at the following wavenumbers: C–H
bending at 730 cm−1 C–C stretching at 1400 cm−1 C–H stretching at 2950 cm−1
Determine the wavenumbers of the possible combination bands and the first
overtones. Fundamental 1st overtone 2nd overtone Figure 1.13 Energy levels for
fundamental and overtone infrared bands. 12 Infrared Spectroscopy:
Fundamentals and Applications 1.4.2 Fermi Resonance The Fermi resonance
effect usually leads to two bands appearing close together when only one is
expected. When an overtone or a combination band has the same frequency as,
or a similar frequency to, a fundamental, two bands appear, split either side of
the expected value and are of about equal intensity. The effect is greatest when
the frequencies match, but it is also present when there is a mismatch of a few
tens of wavenumbers. The two bands are referred to as a Fermi doublet. 1.4.3
Coupling Vibrations in the skeletons of molecules become coupled, as mentioned
in Section 1.4. Such vibrations are not restricted to one or two bonds, but may
involve a large part of the carbon backbone and oxygen or nitrogen atoms if
present. The energy levels mix, hence resulting in the same number of vibrational
modes, but at different frequencies, and bands can no longer be assigned to one
bond. This is very common and occurs when adjacent bonds have similar
1

frequencies. Coupling commonly occurs between C–C stretching, C–O stretching,

Page

C–N stretching, C–H rocking and C–H wagging motions. A further requirement is
that to be strongly coupled, the motions must be in the same part of the
molecule. 1.4.4 Vibration–Rotation Bands When the infrared spectra of gaseous
heteronuclear molecules are analysed at high resolution, a series of closely
spaced components are observed. This type of structure is due to the excitation
of rotational motion during a vibrational transition and is referred to as an
vibration– rotation spectrum [1]. The absorptions fall into groups called branches
and are labelled P, Q and R according to the change in the rotational quantum
number associated with the transition. The separation of the lines appearing in a
vibration– rotation spectrum may be exploited to determine the bond length of
the molecule being examined. Summary The ideas fundamental to an
understanding of infrared spectroscopy were introduced in this chapter. The
electromagnetic spectrum was considered in terms of various atomic and
molecular processes and classical and quantum ideas were introduced. The
vibrations of molecules and how they produce infrared spectra were then
examined. The various factors that are responsible for the position and intensity
of infrared modes were described. Factors such as combination and overtone
bands, Fermi resonance, coupling and vibration– rotation bands can lead to
changes in infrared spectra. An appreciation of these issues is important when
Introduction 13 examining spectra and these factors were outlined in this
chapter. For further reference, there is a range of books and book chapters
available which provide an overview of the theory behind infrared spectroscopy
[3–7].

2
Page
Combination bands, overtones, and Fermi resonances are used to help explain
and assign peaks in vibrational spectra that do not correspond with known
fundamental vibrations. Combination bands and overtones generally have lower
intensities than the fundamentals, and Fermi resonance causes a spilt and shift in
intensity of peaks with similar energies and identical symmetries. Hot bands will
also be briefly addressed.

Introduction
Fundamental vibrational frequencies of a molecule corresponds to transition from
v=0 to v=1. For a non-linear molecule there will by 3N-6 (where N is the number
of atoms) number vibrations. The same holds true for linear molecules, however
the equations 3N-5 is used, because a linear molecule has one less rotational
degrees of freedom.

Figure 1 (below) shows a diagram for a vibrating diatomic molecule. The levels
denoted by vibrational quantum numbers v represent the potenital energy for the
harmonic (quadratic) oscillator. The transition 0→1 is fundamental,
transitions 0→n (n>1) are called overtones, and transitions 1→n (n<1) are called
hot transitions (hot bands).

Figure 1. Potential energy diagram for a vibrating diatomic molecule.

3
Page
Overtones
Overtones occur when a vibrational mode is excited from ν=0 to ν=2, which is
called the first overtone, or ν=0 to ν=3, the second overtone. The fundamental
transitions, v=±1, are the most commonly occurring, and the probability of
overtones rapid decreases as ν=±n increases. The energy of the overtone
transition will be about n times the fundamental associated with that particular
transition. Although the anharmonic oscillator calculations show that the
overtones are usually less than a multiple of the fundamental frequency.
Overtones are generally not detected in larger molecules.
This is demonstrated with the vibrations of the diatomic HCl in the gas phase:

Table 1. HCl vibrational spectrum.

Transition ṽobs [cm-1]
0→1 (fundamental) 2885.9
0→2 (first overtone) 5668.0
0→3 (second overtone) 8347.0
0→4 (third overtone) 10 923.1
0→5 (fourth overtone) 13 396.5

Combination Bands
Combination bands are observed when more than two or more fundamental
vibrations are excited simultaneously. One reason a combination band might
occur is if a fundamental vibration does not occur because of symmetry. This is
comparable to vibronic coupling in electronic transitions in which a fundamental
mode can be excited and allowed as a “doubly excited state.” Combination
implies addition of two frequencies, but it also possible to have a difference band
where the frequencies are subtracted.
4
Page
Hot Bands
Hot bands are observed when an already excited vibration is further excited. For
example an v1 to vn (n = 2,3,….) transition corresponds to a hot band in its IR
spectrum. These transitions are temperature dependent, with lower signal
intensity at lower temperature, and higher signal intensity at higher temperature.
This is because at room temperature only the ground state is highly populated (kT
~ 200 cm-1), based on the Boltzmann distribution.

Fermi Resonances
Fermi resonance results in the splitting of two vibrational bands that have nearly
the same energy and symmetry in both IR and Raman spectroscopies. The two
bands are usually a fundamental vibration and either an overtone or combination
band. The wave functions for the two resonant vibrations mix according to the
harmonic oscillator approximation, and the result is a shift in frequency and a
change in intensity in the spectrum. As a result, two strong bands are observed in
the spectrum, instead of the expected strong and weak bands. It is not possible to
determine the contribution from each vibration because of the resulting mixed
wave function.

If the symmetry requirements are fulfilled and the energies of the two states are
5

similar, mixing occurs, and the resulting modes can be described by a linear
Page

combination of the two interacting modes. The effect of this interaction is to

increase the splitting between the energy levels. The splitting will be larger if the
original energy difference is small and the coupling energy is large. The mixing of
the two states also equalized the intensities of the vibrations which allow a weak
overtone or combination band to show significant intensity from the fundamental
with which it has Fermi resonance with.

Figure 5. Example of intensity and frequency shifts due to Fermi resonance. The
top bands represent two fundamental vibrations without Fermi resonance, and
the bottom bands show the change in bands as a result. The two energy levels are
spilt such that one increases and the other decreases in energy, known as a
“Fermi doublet,” and they move away from each other.
Because the vibrations have nearly the same frequency, the interaction will be
affected if one mode undergoes a frequency shift from deuteration or a solvent
effect while the other does not. The molecule most studied for this type of
resonance (even what Fermi himself used to explain this phenomena), is carbon
dioxide, CO2. The three fundamental vibrations are v 1= 1337 cm-1, v2=667 cm-1,
v3=2349 cm-1. The first overtone of v2 is v1 + 2v2 with symmetries σg+ and (σg+ + δg+),
respectively, and frequencies of 1337 cm -1 (v1) and 2(667) = 1334 cm -1(v2).
According to group theory calculations, CO 2 belongs to the point group D ∞h and
should only have one Raman (symmetric stretching vibrations) and two IR active
modes (asymmetric stretching and bending vibrations). CS 2 is an analog to this
system.
6
Page