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Molecular vibration

Molecular vibration
A molecular vibration occurs when atoms in a molecule are in periodic motion while the molecule as a whole has
constant translational and rotational motion. The frequency of the periodic motion is known as a vibration frequency,
and the typical frequencies of molecular vibrations range from less than 1012 to approximately 1014 Hz.
In general, a molecule with N atoms has 3N – 6 normal modes of vibration, but a linear molecule has 3N – 5 such
modes, as rotation about its molecular axis cannot be observed.[1] A diatomic molecule has one normal mode of
vibration. The normal modes of vibration of polyatomic molecules are independent of each other but each normal
mode will involve simultaneous vibrations of different parts of the molecule such as different chemical bonds.
A molecular vibration is excited when the molecule absorbs a quantum of energy, E, corresponding to the vibration's
frequency, ν, according to the relation E = hν (where h is Planck's constant). A fundamental vibration is excited
when one such quantum of energy is absorbed by the molecule in its ground state. When two quanta are absorbed the
first overtone is excited, and so on to higher overtones.
To a first approximation, the motion in a normal vibration can be described as a kind of simple harmonic motion. In
this approximation, the vibrational energy is a quadratic function (parabola) with respect to the atomic displacements
and the first overtone has twice the frequency of the fundamental. In reality, vibrations are anharmonic and the first
overtone has a frequency that is slightly lower than twice that of the fundamental. Excitation of the higher overtones
involves progressively less and less additional energy and eventually leads to dissociation of the molecule, as the
potential energy of the molecule is more like a Morse potential.
The vibrational states of a molecule can be probed in a variety of ways. The most direct way is through infrared
spectroscopy, as vibrational transitions typically require an amount of energy that corresponds to the infrared region
of the spectrum. Raman spectroscopy, which typically uses visible light, can also be used to measure vibration
frequencies directly. The two techniques are complementary and comparison between the two can provide useful
structural information such as in the case of the rule of mutual exclusion for centrosymmetric molecules.
Vibrational excitation can occur in conjunction with electronic excitation (vibronic transition), giving vibrational
fine structure to electronic transitions, particularly with molecules in the gas state.
Simultaneous excitation of a vibration and rotations gives rise to vibration-rotation spectra.

Vibrational coordinates
The coordinate of a normal vibration is a combination of changes in the positions of atoms in the molecule. When
the vibration is excited the coordinate changes sinusoidally with a frequency ν, the frequency of the vibration.

Internal coordinates
Internal coordinates are of the following types, illustrated with reference to the planar molecule ethylene,

• Stretching: a change in the length of a bond, such as C-H or C-C
• Bending: a change in the angle between two bonds, such as the HCH angle in a methylene group

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In ethene there are 12 internal coordinates: 4 C-H stretching. For example. commonly found in organic compounds. 1 twisting. • Twisting: a change in the angle between the planes of two groups of atoms.Molecular vibration 2 • Rocking: a change in angle between a group of atoms. wagging and twisting as shown here: Symmetrical stretching Asymmetrical stretching Scissoring Rocking Wagging Twisting (These figures do not represent the "recoil" of the C atoms. Symmetry-adapted coordinates Symmetry-adapted coordinates may be created by applying a projection operator to a set of internal coordinates. 2 CH2 wagging. • Out-of-plane: a change in the angle between any one of the C-H bonds and the plane defined by the remaining atoms of the ethylene molecule.[2] The projection operator is constructed with the aid of the character table of the molecular point group. such as a change in the angle between the two methylene groups. Another example is in BF3 when the boron atom moves in and out of the plane of the three fluorine atoms. Note that the H-C-C angles cannot be used as internal coordinates as the angles at each carbon atom cannot all increase at the same time. In a rocking. scissoring. which. 2 CH2 rocking. 2 H-C-H bending. can vibrate in six different ways: symmetric and asymmetric stretching. Vibrations of a Methylene group (-CH2-) in a molecule for illustration The atoms in a CH2 group. such as a methylene group and a plane through the rest of the molecule. Rocking is distinguished from wagging by the fact that the atoms in the group stay in the same plane. the four(un-normalised) C-H stretching coordinates of the molecule ethene are given by where are the internal coordinates for stretching of each of the four C-H bonds. are much smaller than the movements of the lighter H atoms).[3] . The angles do. though necessarily present to balance the overall movements of the molecule. rocking. 1 C-C stretching. Illustrations of symmetry-adapted coordinates for most small molecules can be found in Nakamoto. wagging or twisting coordinate the bond lengths within the groups involved do not change. such as a methylene group and the rest of the molecule. • Wagging: a change in angle between the plane of a group of atoms.

in the linear molecule hydrogen cyanide. The two stretching vibrations are 1. The normal modes can then be qualitatively determined by applying group theory and projecting the irreducible representation onto the cartesian coordinates. normal modes are determined by solving a secular determinant. • symmetric stretching: the sum of the two C-O stretching coordinates. denoted as Q. associated with its own spectrum of quantum mechanical states. Q1 = q1 + a q2 (a << 1) 2. it will belong to a point group.[4] 3 . it is found that the C=O stretches are not independent. and so the normal coordinate refers to the "progress" along that normal mode at any given time. the two C-O bond lengths change by the same amount and the carbon atom is stationary. The advantage of working in normal modes is that they diagonalize the matrix governing the molecular vibrations. principally C-H stretching with a little C-N stretching. Q = q1 + q2 • asymmetric stretching: the difference of the two C-O stretching coordinates. refer to the positions of atoms away from their equilibrium positions. with respect to a normal mode of vibration. and then the normal coordinates (over the normal modes) can be expressed as a summation over the cartesian cordinates (over the atom positions). but rather there is a O=C=O symmetric stretch and an O=C=O asymmetric stretch. when this treatment is applied to CO2. For example.q2 When two or more normal coordinates belong to the same irreducible representation of the molecular point group (colloquially. Each normal mode is assigned a single normal coordinate. If the molecule possesses symmetries. principally C-N stretching with a little C-H stretching. and the normal modes will "transform as" an irreducible representation under that group. one C-O bond length increases while the other decreases. so each normal mode is an independent molecular vibration. HCN.Molecular vibration Normal coordinates The normal coordinates. Formally. Q2 = b q1 + q2 (b << 1) The coefficients a and b are found by performing a full normal coordinate analysis by means of the Wilson GF method. For example. have the same symmetry) there is "mixing" and the coefficients of the combination cannot be determined a priori. Q = q1 .

The hydrogen chloride molecule is attached to the coordinate system to show bond length changes on the curve. When two or more normal vibrations have the same symmetry a full normal coordinate analysis must be performed (see GF method). k.[6] . molecular vibrations can be treated using Newtonian mechanics to calculate the correct vibration frequencies. Since this is one and the same force the ordinary differential equation follows. The vibration frequencies. AB. In the harmonic approximation the spring obeys Hooke's law: the force required to extend the spring is proportional to the extension. μ.Molecular vibration 4 Newtonian mechanics Perhaps surprisingly. In the harmonic approximation the potential energy of the molecule is a quadratic function of the normal coordinate. of the matrix product GF.νi are obtained from the eigenvalues. The anharmonic oscillator is considered elsewhere. the reduced mass of a diatomic molecule. D0 is dissociation energy here. times acceleration. It follows that the force-constant is equal to the second derivative of the potential energy. μ. The solution to this equation of simple harmonic motion is A is the maximum amplitude of the vibration coordinate Q. The proportionality constant is known as a force constant. as The use of the reduced mass ensures that the centre of mass of the molecule is not affected by the vibration. In general. The HCl molecule as an anharmonic oscillator vibrating at energy level E3. r0 bond length. Energy is expressed in wavenumbers.λi. Details concerning the determination of the eigenvalues can be found in.[4] F is a matrix derived from force-constant values. It remains to define the reduced mass.[5] By Newton’s second law of motion this force is also equal to a reduced mass. The basic assumption is that each vibration can be treated as though it corresponds to a spring. is expressed in terms of the atomic masses. U potential energy. G is a matrix of numbers derived from the masses of the atoms and the geometry of the molecule. mA and mB.

evtsz. Wiley. Wiley.phy-astr. Intensities In an infrared spectrum the intensity of an absorption band is proportional to the derivative of the molecular dipole moment with respect to the normal coordinate. the energy states for each normal coordinate are given by .B. Szabó and R. ed.gsu. • Character tables for chemically important point groups (http://symmetry. Saunders. 1997 [4] E.jacobs-university. Knowing the wave functions. Cotton Chemical applications of group theory.de/) .ac. 1962. 1955. 2 . Part A.uk/water/vibrat.C. Vibrational spectroscopy of solids. ISBN 0-08-021022-8 (hardcover) and ISBN 0-08-029141-4 (softcover) [2] F. Pergamon Press.A. Califano.html).bme. 1. Molecular vibrations.. See quantum harmonic oscillator for graphs of the first 5 wave functions. but this does not apply to an anharmonic oscillator.M.. Such a transition gives rise to a hot band. (Reprinted by Dover 1980) [5] S. Vibrating molecules. 5th. Steele.html) • Molecular vibration and absorption (http://www. 1976 [6] P. Cambridge University Press. For example. Nakamoto Infrared and Raman spectra of inorganic and coordination compounds. Chapman and Hall. Scipioni (http://www. Decius and P.A. 1972 External links • Free Molecular Vibration code developed by Zs. 1971 [3] K.Molecular vibration 5 Quantum mechanics In the harmonic approximation the potential energy is a quadratic function of the normal coordinates. 1971 [7] D. Solving the Schrödinger wave equation.B. where n is a quantum number that can take values of 0. Theory of vibrational spectroscopy. edu/Hbase/molecule/vibspe. McGraw-Hill.[7] The intensity of Raman bands depends on polarizability. edition. 1971 Further reading • P. J. Wiley. the observation of overtones is only possible because vibrations are anharmonic. 3rd. The difference in energy when n changes by 1 are therefore equal to the energy derived using classical mechanics. Vibrational states. certain selection rules can be formulated.C. References [1] Landau LD and Lifshitz EM (1976) Mechanics. Sherwood. W. Gans.lsbu. Cross.. for a harmonic oscillator transitions are allowed only when the quantum number n changes by one. Wilson. Another consequence of anharmonicity is that transitions such as between states n=2 and n=1 have slightly less energy than transitions between the ground state and first excited state.html) • small explanation of vibrational spectra and a table including force constants (http://hyperphysics.hu/web/staff/ szabo/web_molecular_vibration/molec_vib_code.

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