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Molecular vibrations

diatomic molecule:

1 2

V kx x R Re

2

potential, the stiffer the bond, the greater the force constant.

curve and k: we expand V(x) around R = Re by a Taylor series:

dV 1 d 2 V 2 1 d 2 V 2

V x V 0 x 2 x ... 2 x

dx 0 2 dx

0

2 dx

0

first derivative of V is 0 at the minimum.

for small displacements we ignore all high terms.

molecular potential energy curve is a

parabolic potential with:

d2 V

k

dx 2

0

if V(x) is wide and shallow, k is small.

Schrödinger equation for the relative motion of two atoms of

masses m1 and m2 with a parabolic potential energy:

2 d2 1 2

kx E

2meff dx 2 2

m1m2

where meff = effective (or reduced) mass: meff

m1 m2

the motion of molecule as a whole.

Example: homonuclear diatomic m1 = m2 = m: meff m / 2.

XH, where mX >> mH: m eff mH .

undergoing harmonic motion. Therefore, the permitted

vibrational energy levels are:

1 k

E n n with: and: n = 0, 1, 2, …

2 meff

discussed for the harmonic oscillator. Important to notice that

En depends on meff and not on the total mass.

Selection rules

vibrational state (absorption or emission):

the electric dipole moment of the molecule

(not necessarily permanent) must change

when the atoms are displaced relative to

one another.

IR active molecules: heteronuclear diatomic.

IR inactive molecules: homonuclear diatomic.

active (e.g.: the symmetric stretch of CO2, in which the C –O–C

bonds stretch and contract symmetrically is inactive.

transition dipole moment and the properties of integrals over

harmonic oscillator wavefunctions, gives (tedious calculation):

Δn 1 absorption

n 1 with

Δn 1 emission

E n 1 E n k m eff

hc hc 2c

generate infrared radiation. The vibrational spectrum provides

the force constant of the bond.

wavenumbers.

Boltzmann: most molecules in their ground states.

dominant spectral transition: fundamental transition 1 0 .

spectrum consists of a single absorption line.

(e.g. , H 2 F2 2HF * ) , transitions 5 4 , 4 3 , … may

also appear (in emission).

all these lines lie at the same frequency

spectrum expected to consist of a single line.

NO! Breakdown of the harmonic approximation.

Anharmonicity

Harmonic oscillator is only a parabolic approximation to the

actual molecular potential energy curve:

does not allow a bond to dissociate.

at high vibrational excitations, not enough spread of the

vibrational wavefunction.

be retained.

proportional to the displacement)

can anticipate that the energy levels become less widely

spaced at high excitations.

Morse potential energy:

V hcDe 1 e

a (R R e ) 2

1/ 2

meff 2

with a

2hcDe

allows for dissociation at large displacements.

Schrödinger equation can be solved

and the permitted energy levels are:

2

1 1

E n n n x e

2 2

a 2

with x e

2m eff 4D e

xe = anharmonicity constant.

2nd term in En substracts from 1st with increasing effect as n

increases. Hence, convergence of the levels at high quantum

numbers.

practice we fit the experimental data with the more general

expression:

2 3

1 1 1

E n n n x e n y e ...

2 2 2

the molecule allowing to find its dissociation energy.

Wavenumbers: 2(n 1)x e ...

hc hc

Anharmonicity accounts for the appearance of additional weak

absorption lines (transitions 2 0 or 3 0 ,…) even though

these overtones are forbidden by the selection rule n = ±1.

wavefunctions approximation! All n values allowed, but n

> 1 transitions allowed only weakly if anharmonicity is slight.

is used to determine the dissociation

energy, D0, of the bond if we write

En+1/2 = En+1-En ( n 1 n ) then:

D 0 E1/ 2 E 3 / 2 ...

E n 1/ 2

n

En+1/2 against n+1/2

taken into account.

inaccessible part of the spectrum

estimated by linear extrapolation.

most actual plots are not linear (as

shown here) so the D0 value obtained

is an overestimate.

Vibration-Rotation

spectra

High resolution vibrational

spectrum of gas-phase HCl

each line = large number of closely spaced components.

separation < 10 cm-1 suggestive of rotational transitions.

leads to a sudden increase/decrease in instantaneous bond

length. Therefore, rotation is retarded/accelerated by a

vibrational transition (think “ice-skaters”).

vibration and rotation changes shows that the rotational

quantum number J changes by ±1 during the vibrational

transition. If the molecule also possesses angular momentum

about its axis, then the selection rules also allow J = 0.

of the combination (ignoring anharmonicity and centrifugal

distortion):

1

E n,J E n E J n BJ (J 1)

2

B should depend on the vibrational state because, as n

increases, the molecule swells slightly and the moment of

inertia changes. We will ignore this for the time being.

±1 and in some cases by 0 (when J = 0 is allowed). The

absorptions then fall into three groups called branches of the

spectrum:

vibrational transition . (Forbidden in

HCl, hence the gap.)

levels and the magnitude of the J 1 J transition moment.

vibrational transition gives the value of B (or B), hence the

bond length (as with a pure rotational microwave spectrum).

Combination differences

Anharmonicity : B1<B0 in general (because extended bond)

Q branch (if it exists): series of closely spaced lines.

R branch: lines converge slightly as J increases.

P branch: lines diverge.

P J B1 B0 J B1 B0 J 2

Hence: Q J B1 B0 J J 1

R J B1 B0 J 1 B1 B0 J 12

individually (widely used in spectroscopy):

state, dependence on B0 only:

1

R J 1 P J 1 4B0 J

2

common lower state, dependence on B1

only:

1

R J P J 4B1 J

2

difference against J+½ straight line

of slope 4B0 (any deviation from

straight line = consequence of

centrifugal distortion).

= 10.440 cm-1 and B 1 = 10.136 cm-1.

Vibrational Raman spectra of diatomic molecules

change as molecule vibrates. Hence, both homo- and hetero-

nuclear diatomic molecules are vibrationally Raman active.

lines to high of incident radiation (anti-Stokes): n = –1.

lines to low of incident radiation (Stokes): n = +1.

involved in transition, hence anti-Stokes lines (excited states)

are weaker.

a branch structure arising from

rotational transitions accompanying the

vibrational excitation.

Raman): J = 0, ±2: O branch: J=–2;

Q branch: J=0; S branch: J=+2.

O J i 2B 4BJ

Hence: Q J i

S J i 6B 4BJ

molecules!

The vibrations of

polyatomic molecules

Diatomic molecule = one vibrational mode: the bond stretch.

Polyatomic molecule = several modes of vibrations: all bonds

and angles.

Normal modes

nonlinear: 3N – 6 independent vibrational modes.

linear: 3N – 5 independent vibrational modes.

3N coordinates (x,y,z for each atom). With

physically sensible grouping:

of centre of mass.

2 angles needed for special orientation of

molecular axis.

1 angle (if nonlinear!) needed for

orientation around the molecular axis.

the remaining are vibrational modes.

Examples:

CO2 = linear triatomic, 4 vibration modes, 2 rotation modes.

Naphthalene C10H8 = 48 distinct modes of vibration.

A possible choice for the 4 modes of CO2:

stretching of the other bond (R),

and 2 perpendicular bend modes (2).

forwards between L and R); position of centre of mass varies.

1 = symmetric stretch

3 = antisymmetric stretch

2 (2x) = bending modes

excite the other.

group of atoms that may be excited without leading to the

excitation of any other normal mode and without involving

translation or rotation of the molecule as a whole.

Each normal mode, q, behaves like an independent harmonic

oscillator (if anharmonicities are neglected), with:

1 1 k q mq

E n (q) n q n hc q with

2 2 2c

mode q; mq = effective mass for the mode q.

swung about by the vibration = complicated function of the

masses of the atoms. Example for CO2:

masses of only the O atoms.

so all contribute to mq.

than those of stretching modes.

and bending of bonds (not the case for

CO2).

Infrared absorption spectra

of polyatomic molecules

Gross selection rule for infrared activity of a normal mode: it

should be accompanied by a change of dipole moment.

Decided by inspection. Example, for CO2:

unchanged (at zero)

antisymmetric stretch is infrared active: dipole moment

changes parallel to molecular axis because molecule

becomes unsymmetrical as it vibrates; parallel band.

both bending modes are infrared active: dipole moment

changes perpendicular to the principal axis; perpendicular

band. Molecular linearity eliminated, hence a Q branch is

observed.

approximation).

various parts of the molecule, that is, its force field = set of

force constants corresponding to all displacements of the

atoms.

hindered in liquids or solids).

rotational energies are ill-defined:

lifetime broadening > 1 cm-1 can easily result.

rotational structure of vibrational spectrum is blurred.

infrared spectra in condensed phases usually consists

of broad lines spanning the entire range of the resolved

gas-phase spectrum, and showing no branch structure.

Vibrational Raman spectra

of polyatomic molecules

Gross selection rule for vibrational Raman activity of a normal

mode: it should be accompanied by a changing polarizability.

Decided by inspection (usually difficult). Example, for CO2:

contraction changes polarizability.

other modes are Raman inactive.

has a centre of symmetry, then no modes can be both infrared

and Raman active. A mode may be inactive in both. This rule

applies to CO2, but not H2O or CH4.

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