Molecular Spectroscopy Crib Sheet

Units
In molecular spectroscopy it is common to report energies in wavenumbers,
Ẽ cm−1 , rather than Joules (E). The two are related through

Ẽ = E/hc

where the Planck constant, h = 6.626 × 10−34 J s and the speed of light must
be taken in cm s−1 : c = 2.998 × 1010 cm s−1 , of course.
The reason for this convention is that the resonance condition for a photon of
frequency ν s−1 to bring about a transition between two states separated by an
energy ∆E J is hν = ∆E , so the photon’s wavenumber, ν̃ = ν/c = ∆E/hc is
proportional to the energy difference and has convenient orders of magnitude
for most spectroscopic applications.
Accordingly, energy levels (strictly, term values) are given below in wavenumber
units.

Rotational Spectroscopy
The energy levels of a diatomic molecule A-B, treated as a rigid rotor are given
in terms of a quantum number, J:

ẼJ = BJ(J + 1), J = 0, 1, 2, . . .

where the rotational constant (in cm−1 ) is

h mA mB
B= , I = µr2 , µ=
8π 2 Ic mA + m B

and I is the moment of inertia of the molecule in terms of its reduced mass, µ,
and bond length, r.
There is no zero-point energy (Ẽ0 = 0), and each energy level has degeneracy

gJ = 2J + 1

For a molecule to show a pure rotation spectrum it must have a permanent

electric dipole moment. The selection rule on J is then ∆J = ±1 , and the ab-
sorption spectrum is observed as lines (equally spaced by 2B) in the microwave
region of the electromagnetic spectrum:

ν̃J+1←J = ẼJ+1 − ẼJ = 2B(J + 1)

Centrifugal distortion occurs when the bond is stretched at high angular veloci-
ties. As r increases, I increases, and so B decreases: the lines get closer together
in the spectrum. To a first approximation, this effect can be accounted for by
the inclusion of a small, positive constant D in the energy level expression:

ẼJ = BJ(J + 1) − DJ 2 (J + 1)2

Vibrational Spectroscopy
The energy levels of a diatomic molecule treated as a harmonic oscillator are
given in terms of a quantum number, v:

Ẽv = ν̃(v + 12 ), v = 0, 1, 2, . . .

where the fundamental vibrational wavenumber, ν̃, is given (in cm−1 ) by

s
1 k
ν̃ =
2πc µ

where k is the bond force constant. There is zero-point energy (Ẽ0 = 12 ν̃), and
the energy levels are non-degenerate (gv = 1).
To show an infrared vibrational spectrum, there must be a change in the molecule’s
dipole moment on vibration. The selection rule on v is then ∆v = ±1 , so the
absorption spectrum consists of a single line at a wavenumber

ν̃v+1←v = Ẽv+1 − Ẽv = ν̃

A real molecule is anharmonic: the vibrational energy levels converge as v in-

creases, and the molecule dissociates at high vibrational excitation. The Morse
oscillator is better approximation than the harmonic oscillator:

Ẽv = ω̃e (v + 21 ) − ω̃e xe (v + 12 )2

where ω̃e is the equilibrium vibrational wavenumber - the hypothetical frequency

of infinitely small vibrations about the equilibrium geometry (r = re , at the
bottom of the potential well), and xe is the anharmonicity constant, a small,
positive parameter related to the dissociation energy, D̃e , measured from the
bottom of the potential well:
ω̃e
xe =
4D̃e
The strongest infrared absorption signal corresponds to the fundamental tran-
sition v = 1 ← v = 0, at:
ν̃1←0 = ω̃e − 2ω̃e xe
The selection rule for an anharmonic oscillator also allows for transitions with
∆v = ±2, ±4, . . . corresponding to overtones. For example,
ν̃2←0 = 2ω̃e − 6ω̃e xe
Hot bands are vibrational transitions originating from v 6= 0, and appear at
slightly lower frequency than the fundamental. They are generally weak because
the populations of the v = 1, 2, . . . levels are much smaller than the population
of the ground v = 0 level. For example,
ν̃2←1 = ω̃e − 4ω̃e xe
From the wavenumbers of several (∆v = +1) transitions it is common to define
the quantity
∆Gv+ 21 = ν̃v+1←v = ω̃e − 2(v + 1)ω̃e xe
A plot of ∆Gv+ 12 against v + 21 is a straight line (to this level of approximation)
which intersects the abscissa at vmax + 21 , where the vibrational levels converge.
An estimate of the dissociation energy relative to the v = 0 level, D̃0 , can be
obtained as the area under this Birge-Sponer plot of ∆Gv+ 12 .
Polyatomic molecules: For a non-linear N -atomic molecule there are 3N − 6
normal vibrational modes. For a linear molecule, there are 3N − 5 modes.

Vibration-Rotation Spectroscopy
At high-resolution, vibrational transitions appear in spectra as bands of lines due
to rotational transitions (J ′ ← J”) occurring simultaneously with the change in
vibrational quantum number (v ′ ← v”).
The energy levels can be written

Ẽv,J = ν̃(v + 12 ) + BJ(J + 1)

and the selection rule ∆J = ±1 (for closed-shell diatomics) gives rise to two
branches of lines: R (∆J = +1) and P (∆J = −1). So the band structure of a
vibrational transition (v + 1 ← v) shows lines at:

ν̃P(J) = ν̃ − 2BJ and ν̃R(J) = ν̃ + 2B(J + 1)

In the notation P(J) and R(J), the quantum number J refers to the lower state
of the transition.
A Q-branch (∆J = 0) is only seen in molecules which have a source of angular
momentum other than rotation of the nuclear framework (e.g. NO, which has
electronic orbital angular momentum). Q-branches are generally strong, partly
because they consist of many overlapping lines (at ν̃Q(J) = ν̃).
In fact, the rotational constant, B, is not the same in the two vibrational states
(because the bond-length, r changes because of anharmonicity), and so the
rotational lines are not evenly spaced in the vibrational band. To a first ap-
proximation, Bv may be written

Bv = Be − α(v + 12 )

where α is a small, positive constant called the vibration-rotation interaction

constant and Be is the hypothetical rotational constant at the bond length of
the bottom of the potential well (cf. ωe ).
Bv may be obtained for the two vibrational states by taking combination dif-
ferences: the difference in wavenumber between two transitions with a common
upper state (v + 1, J ′ ) depends only on Bv , the rotational constant for the lower
vibrational level and the difference between two transitions with a common
lower state (v, J”) depends only on Bv+1 . Therefore, for the v = 1 ← v = 0
vibrational band:

ν̃R(J−1) − ν̃P(J+1) = 4B0 (J + 21 ) and ν̃R(J) − ν̃P(J) = 4B1 (J + 12 )

Each infrared-active normal mode of a polyatomic molecule shows band struc-

ture in its vibrational spectrum. If the vibration gives rise to a change in dipole
moment along the molecular axis (e.g. the asymmetric stretch in CO2 ), the
selection rule ∆J = ±1 applies; if the change in dipole moment is perpendicular
to the molecular axis (i.e. a bending vibration), ∆J = 0, ±1 - a Q-branch is
seen in the spectrum.

Rotational Raman Spectroscopy

For a molecule to show a pure rotational Raman spectrum it must be anisotrop-
ically polaraizable (e.g. all diatomics, but not atoms or spherical rotors such as
CH4 . Raman spectroscopy is based on the inelastic scattering of incident laser
light of frequency νi . The selection rule for linear molecules is ∆J = 0, ±2 .
Rayleigh scattering, corresponding to ∆J = 0 is elastic; inelastic scattering
leading to molecular excitation (∆J = +2, photons scattered at frequencies
ν < νi ) is referred to as Stokes scattering and that leading to molecular de-
excitation (∆J = −2, ν > νi ) is anti-Stokes scattering. The wavenumbers of
the scattered photons are therefore:

ν̃J+2←J = ν̃i − 2B(2J + 3) and ν̃J−2←J = ν̃i + 2B(2J − 1)

and the rotational Raman lines are spaced by 4B.

Vibrational Raman Spectroscopy

The gross selection rule for vibrational Raman scattering is that the polarizabil-
ity must change as the molecule vibrates. Thus, homonuclear diatomic molecules
show a Raman spectrum even though they do not show an infrared absorption
spectrum. The selection rule is ∆v = ±1 , though the anti-Stokes vibrational
lines (∆v = −1) are usually weak because of the low populations of excited
vibrational states.
Vibrational transitions may occur simultaneously with rotational transitions
according to the above selection rule, ∆J = 0, ±2, leading to O, Q, and S
branches at high resolution:

ν̃O(J) = ν̃i − ν̃ − 2B + 4BJ ν̃Q(J) = ν̃i − ν̃ ν̃S(J) = ν̃i − ν̃ − 6B − 4BJ

A useful rule for assigning bands in a polyatomic molecule is the rule of mutual
exclusion: if a molecule has a centre of symmetry, then no modes are both
infrared and Raman active (though a mode may be inactive in both).