3.
5 THE VIBRATIONS OF POLYATOMIC MOLECULES
• We shall need to discuss:
• 1. The number of fundamental vibrations and their symmetry.
• 2. The possibility of overtone and combination bands.
• 3. The influence of rotation on the spectra.
• 3.5.1 Fundamental Vibrations and Their Symmetry
Translational motion and its degree of freedom
• Translational motion of a molecule is the bodily movement of the molecule from one place to another.
• During translation, the center of gravity of the molecule defined by the translational vector changes.
• The three components of the translational vector are the three Cartesian coordinates x,y and z , sometimes
designated as Tx, Ty and Tz
• Thus the degree of freedom for translational motion of a molecule is always 3
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Rotational motion and its degree of freedom
• All molecules rotate about an axis passing through their center of gravity
• The complex rotational motion of a molecule can be conveniently resolved into three rotational components
about three mutually perpendicular directions through the center of gravity.
• The three components of the rotation vector are designated Rx, Ry and Rz
• The degree of freedom for the rotational motion of a non linear molecule is always 3
• However for a linear molecule, the rotational degree of freedom is only 2. In the case of linear molecules
the rotation about the bond axis is not counted as the moment of inertia for rotation about the bond axis is
zero
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Vibrational motion and its degree of freedom
• Vibrational motion of a molecule involves stretching and compression of bonds.
• THE VIBRATIONAL DEGREE OF FREEDOM OF A MOLECULE IS OBTAINED BY SUBTRACTING THE SUM OF THE
TRANSLATIONAL AND ROTATIONAL DEGREES OF FREEDOM FROM THE TOTAL DEGREE OF FREEDOM OF THE
MOLECULE
• The total degree of freedom for a molecule with N atoms is 3N (three for each atom) . Recall the set of
vectors basis for the generation of RRs
• Translational degree of freedom + Rotational degree of freedom = 3 + 3 = 6 for Non linear molecules
• Translational degree of freedom + Rotational degree of freedom = 3 + 2 = 5 for Linear molecules
• Therefore
Vibrational degree of freedom or Number of modes of vibration = 3N − 6 for Non linear molecules
Vibrational degree of freedom or Number of modes of vibration = 3N − 5 for Linear molecules
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• Let us look briefly at examples of these rules.
• First, we see that for a diatomic molecule (perforce linear) such as we have already considered in this
chapter, N = 2, 3N - 5 = 1 and thus there can be only one fundamental vibration.
• Note, however, that the 3N - 5 rule says nothing about the presence, absence, or intensity of overtone
vibrations-these are governed solely by anharmonicity.
• Next, consider water, H20. This (Fig. 3.9) is non-linear and triatomic. Also in the figure are the 3N - 6 = 3
allowed vibrational modes, the arrows attached to each atom showing the direction of its motion during half
of the vibration. Each motion is described as stretching or bending depending on the nature of the change in
molecular shape.
• These three vibrational motions are also referred to as the normal modes of vibration (or normal vibrations)
of the molecule.
• In general a normal vibration is defined as a molecular motion in which all the atoms oscillate with the same
frequency and pass through their equilibrium positions simultaneously.
• Further, each motion of Fig. 3.9 is labelled either symmetric or antisymmetric.
• It is not necessary here to go far into the matter of general molecular symmetry since other excellent texts
already exist for the interested student, but we can see quite readily that the water molecule contains some
elements of symmetry.
• In particular consider the dashed line at the top of Fig. 3.9 which bisects the HOH angle; if we rotate the
molecule about this axis by 180" its final appearance is identical with the initial one.
• This axis is thus referred to as a C2 axis since twice in every complete revolution the molecule presents an
identical aspect to an observer.
• This particular molecule has only the one rotational symmetry axis, and it is conventional to refer the
molecular vibrations to this axis.
• Thus consider the first vibration (Fig. 3.9(a)). If we rotate the vibrating molecule by 180" the vibration is
quite unchanged in character-we call this a symmetric vibration.
• The bending vibration, v2, is also symmetric. Rotation of the stretching motion of Fig. 3.9(c) about the C2
axis, however, produces a vibration which is in antiphase with the original and so this motion is described as
the antisymmetric stretching mode.
• In order to be infra-red active, as we have seen, there must be a dipole change during the vibration and this
change may take place either along the line of the symmetry axis (parallel to it, or 11) or at right angles to
the line (perpendicular, I).
• Figure 3.10 shows the nature of the dipole changes for the three vibrations of water, and justifies the labels
parallel or perpendicular attached to them in Fig. 3.9. We shall see later that the distinction is important
when considering the influence of rotation on the spectrum.
• Finally the vibrations are labelled in Fig. 3.9 as 𝜈 1, 𝜈 2, and 𝜈 3.
• By convention it is usual to label vibrations in decreasing frequency within their symmetry type.
• Thus the symmetric vibrations of H20 are labelled 𝜈 1 for the highest fully symmetric frequency (3651.7 cm-1)
and 𝜈 2 for the next highest (1595.0 cm-1); the antisymmetric vibration at 3755.8 cm-1 is then labelled 𝜈 3.
• Our final example is of the linear triatomic molecule CO2, for which the normal vibrations are shown in Fig.
3.11.
• For this molecule there are two different sets of symmetry axes.
• There is an infinite number of twofold axes (C2) passing through the carbon atom at right angles to the bond
direction, and there is an ∞-fold axis (C∞,) passing through the bond axis itself (this is referred to as ∞-fold
since rotation of the molecule about the bond axis through any angle gives an identical aspect).
• The names symmetric stretch and antisymmetric stretch are self-evident, but it should be noted that the
symmetric stretch produces no change in the dipole moment (which remains zero) so that this vibration is not
infra-red active.
• This vibration frequency may be obtained in other ways, however, which we shall discuss in the next chapter.
• For linear triatomic molecules, 3N - 5 = 4, and we would expect four vibrational modes instead of the three
shown in Fig. 3.11.
• However, consideration shows that 𝜈 2 in fact consists of two vibrations-one in the plane of the paper as drawn
and the other in which the oxygen atoms move simultaneously into and out of the plane.
• The two sorts of motion are, of course, identical in all respects except direction and are termed degenerate;
they must, nevertheless, be considered as separate motions, and it is always in the degeneracy of a bending
mode that the extra vibration of a linear molecule over a non-linear one is to be found.
3.5.2 Overtone and Combination Frequencies
• If one were able to observe the molecules of H20 or C02 directly their overall vibrations would appear
extremely complex.
• In particular, each atom would not follow tidily any one of the separate paths depicted in Figs 3.9 or 3.1 1,
but its motion would essentially be a superposition of all such paths, since every possible vibration is always
excited, at least to the extent of its zeropoint energy.
• However, such superposition could be resolved into its components if, for instance, we could examine the
molecules under stroboscopic light flashing at each fundamental frequency in turn.
• This is, so to speak, the essence of infra-red spectroscopy-instead of flashing we have the radiation
frequency, and the 'examination' is a sensing of dipole alteration.
• Thus, as we would expect, the infra-red spectrum of a complex molecule consists essentially of an absorption
band at each of the 3N - 6 (non-linear) or 3N - 5 (linear) fundamental frequencies.
• This is, of course, an over-simplification, in which two approximations are implicit: (1) that each vibration is
simple harmonic, (2) that each vibration is quite independent and unaffected by the others.
• We shall consider (2) in more detail later; for the moment we can accept it as a good working approximation.
• When the restriction to simple harmonic motion is lifted we have again, as in the case of the diatomic
molecule (Sec. 3.1.3), the possibility of first, second, etc., overtones occurring at frequencies near 2𝜈 1, 3𝜈 1, .
. . , 2𝜈 2, 3𝜈 2, . . . , 2𝜈 3, . . . , etc., where each 𝜈 i is a fundamental mode.
• The intensities fall off rapidly.
• However, in addition, the selection rules now permit combination bands and difference bands.
• The former arise simply from the addition of two or more fundamental frequencies or overtones.
• Such combinations as 𝜈 1 + 𝜈 2, 2 𝜈 1 + 𝜈 2, 𝜈 1 + 𝜈 2 + 𝜈 3, etc., become allowed, although their intensities are
normally very small.
• Similarly the difference bands, for example, 𝜈 1 - 𝜈 2, 2 𝜈 1 - 𝜈 2, 𝜈 1 + 𝜈 2 - 𝜈 3, have small intensities but are often
to be found in a complex spectrum.
• The intensities of overtone or combination bands may sometimes be considerably enhanced by a resonance
phenomenon.
• It may happen that two vibrational modes in a particular molecule have frequencies very close to each other-
they are described as accidentally degenerate.
• Note that we are not here referring to identical vibrations, such as the two identical 𝜈 2 's of C02 (Fig. 3.11),
but rather to the possibility of two quite different modes having similar energies.
• Normally the fundamental modes are quite different from each other and accidental degeneracy is found
most often between a fundamental and some overtone or combination.
• A simple example is to be found in C02 where 𝜈 1, described as at about 1330 cm-1, is very close to that of 2𝜈 2
= 1334 cm-1.
• (As mentioned earlier, these bands are not observable in the infra-red, but both may be seen in the Raman
spectrum discussed in the next chapter; the principles of resonance apply equally to both techniques.)
• Quantum mechanics shows that two such bands may interfere with each other in such a way that the higher is
raised in frequency, the lower depressed-and in fact the Raman spectrum shows two bands, one at 1285 cm-1 ,
the other at 1385 cm-1 .
• Their mean is plainly at about 1330 cm-1 .
• Note, however, that one of these bands arises from a fundamental mode (𝜈 1), the other from the overtone
2 𝜈 2, and we would normally expect the former to be much more intense than the latter.
• In fact, they are found to be of about the same intensity-the overtone has gained intensity at the expense of
the fundamental.
• This is an extreme case-normally the overtone takes only a small part of the intensity from the fundamental.
• The situation is often likened to that of two pendulums connected to a common bar-when the pendulums have
quite different frequencies they oscillate independently.
• When their frequencies are similar they can readily exchange energy, one with the other, and an oscillation
given to one is transferred to and fro between them.
• They are said to resonate.
• Similarly two close molecular vibrational frequencies resonate and exchange energy-the phenomenon being
known as Fermi resonance when a fundamental resonates with an overtone.
• In the spectrum of a complex molecule exhibiting many fundamentals and overtones, there is a good chance of
accidental degeneracy, and Fermi resonance, occurring.
• However, it should be mentioned that not all such degeneracies lead to resonance. It is necessary, also, to
consider the molecular symmetry and the type of degenerate vibrations; we shall not, however, pursue the
topic further here.
3.6 THE INFLUENCE OF ROTATION ON THE SPECTRA OF POLYATOMIC MOLECULES
• In Sec. 3.2 we found that the selection rule for the simultaneous rotation and vibration of a diatomic
molecule was
• and that this gave rise to a spectrum consisting of approximately equally spaced line series on each side of a
central minimum designated as the band centre.
• Earlier in the present section we showed that the vibrations of complex molecules could be subdivided into
those causing a dipole change either (1) parallel or (2) perpendicular to the major axis of rotational
symmetry.
• The purpose of this distinction, and the reason for repeating it here, is that the selection rules for the
rotational transitions of complex molecules depend, rather surprisingly, on the type of vibration, 11 or I,
which the molecule is undergoing. Less
Refer Banwell for further details.
3.7 ANALYSIS BY INFRA-RED TECHNIQUES
• Because of the 3N - 6 and 3N - 5 rules it is evident that a complex molecule is likely to have an infra-red
spectrum exhibiting a large number of normal vibrations.
• Each normal mode involves some displacement of all, or nearly all, the atoms in the molecule, but while in
some of the modes all atoms may undergo approximately the same displacement, in others the displacements
of a small group of atoms may be much more vigorous than those of the remainder.
• Thus we may divide the normal modes into two classes:
• the skeletal vibrations, which involve many of the atoms to much the same extent,
• and the characteristic group vibrations, which involve only a small portion of the molecule, the remainder
being more or less stationary.
• We deal with these classes separately.
3.7.1 Skeletal Vibrations
• For organic molecules these usually fall in the range 1400-700 cm -1 and arise from linear or branched chain
structures in the molecule. Thus such groups as
• etc., each give rise to several skeletal modes of vibration and hence several absorption bands in the infra-
red.
• It is seldom possible to assign particular bands to specific vibrational modes, but the whole complex of bands
observed is highly typical of the molecular structure under examination.
• Further, changing a substituent (on the chain, or in the ring) usually results in a marked change in the pattern
of the absorption bands.
• Thus these bands are often referred to as the 'fingerprint' bands, because a molecule or structural moiety
may often be recognized merely from the appearance of this part of the spectrum.
• One example of infra-red (IR) spectroscopy as a fingerprint technique is shown in Fig. 3.19(a). The late 1970s
saw the launch of Voyager space probes to observe the giant planets Jupiter, Saturn, Uranus, and Neptune.
The probes were equipped with a number of spectrometers in order to gather as much information as
possible.
• The atmospheres of these planets are mostly composed of hydrogen and helium, but IR spectroscopy proved
to be extremely useful for the determination of some of the other constituents.
• Figure 3.19(a) shows the IR emission spectra of Saturn and Jupiter, together with the assignment of the major
peaks.
• Another excellent example of IR as a fingerprint technique is shown in Fig. 3.19(b), which compares the
spectra of natural and synthetic thymidine. The remarkably exact correlation between the spectra proves
that the synthetic product does not differ in the slightest degree from the natural substance.
