____________________________________________________________________________________________________

Subject Chemistry

Paper No and Title 8 and Physical Spectroscopy

Module No and Title 5 and Transition probabilities and transition dipole moment,
Overview of selection rules
Module Tag CHE_P8_M5

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 5 (TRANSITION PROBABILITIES AND
TRANSITION DIPOLE MOMENT. OVERVIEW OF
SELECTION RULES)
____________________________________________________________________________________________________

TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Transition Moment Integral
4. Overview of Selection Rules

5. Summary

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 5 (TRANSITION PROBABILITIES AND
TRANSITION DIPOLE MOMENT. OVERVIEW OF
SELECTION RULES)
____________________________________________________________________________________________________

1. Learning Outcomes
After studying this module,

• you shall be able to understand the basis of selection rules in spectroscopy

• Get an idea about how they are deduced.

2. Introduction
The intensity of a transition is proportional to the difference in the populations of the initial and
final levels, the transition probabilities given by Einstein’s coefficients of induced absorption and
emission and to the energy density of the incident radiation. We now examine the Einstein’s
coefficients in some detail.

3. Transition Dipole Moment

Detailed algebra involving the time-dependent perturbation theory allows us to derive a
theoretical expression for the Einstein coefficient of induced absorption
! 2
M ij 8π 3 ! 2
Bij = 2
= 2
M ij
6ε 0 " 3h (4πε 0 )
where the radiation density is expressed in units of Hz.
!
The quantity M ij is known as the transition moment integral, having the same unit as dipole
moment, i.e. C m. Apparently, if this quantity is zero for a particular transition, the transition
probability will be zero, or, in other words, the transition is forbidden. This forms the basis for the
selection rules for transitions.

Selection rules tell us the possible transitions among quantum levels due to absorption or
emission of electromagnetic radiation. Incident electromagnetic radiation presents an oscillating
electric field E0cos(ωt) that interacts with a transition dipole. The dipole moment vector
! ! !
is µ = er , where r is a vector pointing in a direction of space.

By definition, the dipole moments of two given states i and j are

! +∞
M ii = ψ i* µˆψ i dτ
∫
−∞

and

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 5 (TRANSITION PROBABILITIES AND
TRANSITION DIPOLE MOMENT. OVERVIEW OF
SELECTION RULES)
____________________________________________________________________________________________________

! +∞
M jj = ψ *j µˆψ j dτ
∫
−∞

respectively.

! +∞
The symbol M ij = ψ *j µˆψ i dτ signifies the transition dipole moment for a transition from the i
∫
−∞
state to the j state, and signifies a transient dipolar polarization created by an interaction of
electromagnetic radiation with a molecule.

4. Overview of Selection Rules

!
M ij is a triple integral involving the complex conjugate of the excited state wave
function, the dipole moment operator and the wave function of the ground state. Though
the quantum mechanical solution of wave functions for the ground and excited states is
complicated, it is often possible to deduce the selection rules from the symmetry
properties of the wave functions alone.

From well-known fact of mathematics, that a function f(x), which reverses sign on
replacing x by –x is an odd function, and a function which does not change sign under a
similar operation is an even function. Some examples of odd functions are

f ( x) = x + 3 x 3 ; f ( x) = 2 x 3 + 3x 5 + 5 x 7

You may note that all powers of x in such expressions are odd, so that the function
changes sign on reversing the sign of x; in other words, f(-x) = f(x).

Similarly, functions having all even powers of x are even functions, and for these f(-x) =
f(x). Examples are f(x) = x2 and f(x) = 2x4 + x6.

On the other hand, functions such as f(x) = 2x4 + x5

are neither even nor odd, and possess no symmetry
properties.

The figure on the right is a plot of an even function (y

= x2). It is also a well-known fact of mathematics that
+a
the integral ∫ ydx represents the area under the curve
−a
of y against x between the two limits. It is apparent
CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)
MODULE No. : 5 (TRANSITION PROBABILITIES AND
TRANSITION DIPOLE MOMENT. OVERVIEW OF
SELECTION RULES)
____________________________________________________________________________________________________

that this is just twice the integral between the limits 0 and a, and is non-zero.

Now, let us examine a similar graph for an

odd function, y = x3. The figure on the left
shows that the area is positive for positive
values of x and negative for negative values
of x, so that the integral between –a and a
vanishes because of the cancellation of the
positive and negative areas.

Exactly the same reasoning applies for

deducing the selection rules from the
transition moment integral. If the triple product is an odd function, it will vanish on
integration and the corresponding transition will be forbidden. Similarly, if the triple
product is even, the transition may be allowed.

Wave functions that do not change sign on reflection (r → -r) are said to be of even
parity and those that change sign are of odd parity. The dipole moment operator
transforms as r, since for a single electron, the dipole moment operator is er, where e is
the electronic charge. Thus it is of odd parity. For the transition moment integral to
survive, therefore, the product of the two wave functions should also be of odd parity,
since odd × odd = even. This is only possible if one is odd and the other even, since odd
× even = odd. We immediately have the Laporte selection rule, which states that the wave
function should change its parity during a transition.

This rule is also stated as follows: g ↔ u, but g ↮   g  and u ↮ u. This notation originates
from the German gerade for wave functions of even parity, denoted as g, and ungerade
for wave function of odd parity (denoted by u), in the case of centrosymmetric molecules.

An immediate application of this rule is in atomic spectroscopy. Consider the atomic

orbitals shown below:

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 5 (TRANSITION PROBABILITIES AND
TRANSITION DIPOLE MOMENT. OVERVIEW OF
SELECTION RULES)
____________________________________________________________________________________________________

It is apparent that the s and d orbitals are of even parity and hence transitions cannot take
place between them. However, the p orbitals are of odd parity and hence transitions
between the s and p orbitals may be possible. Though these are allowed transitions by
electric dipole selection rules, the argument does not explain why s to f transitions are
forbidden, though these transitions involve a change of parity. It is important to
remember that the symmetry selection rules only tell us which transitions are forbidden
by symmetry, but it does not follow that the remaining transitions are allowed. They may
be forbidden for reasons other than symmetry. In the present case, conservation of
angular momentum requires that the angular momenta of the atom and photon should
remain constant. Since the photon has an intrinsic angular momentum of one, it can either
add one unit or subtract one unit of angular momentum from the atom. In other words,
the l quantum number can either decrease or increase by one unit, or Δl = ±1. Hence, an s
electron can only be promoted to a p orbital.

Every kind of spectroscopy has two parts to the selection rules: a gross selection rule and
a specific selection rule. The gross selection rule states the requirements for an atom or
molecule to display a particular spectrum and the specific selection rule states the
changes in quantum numbers accompanying the transitions. The gross selection rule is
often easy to predict based on the requirements for effective interaction with the
electromagnetic field.

Rotational spectroscopy

A molecule must have a transition dipole moment that is in resonance with the electromagnetic
field for rotational spectroscopy to be used. Polar molecules have a dipole moment and are thus
microwave active. The term means that they will exhibit rotational spectra, which is usually
observed in the microwave region.

As the molecule rotates, the dipole moment vector also oscillates. If the oscillation is in
resonance with the electric field, absorption or emission of radiation is induced. In
contrast, a homonuclear diatomic molecule like N2 or F2 possesses no permanent dipole
moment and is hence microwave inactive. Molecules having a spherical shape, such as
CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)
MODULE No. : 5 (TRANSITION PROBABILITIES AND
TRANSITION DIPOLE MOMENT. OVERVIEW OF
SELECTION RULES)
____________________________________________________________________________________________________

the tetrahedral molecule SiH4, are also microwave inactive for the same reason. However,
when the molecule undergoes fast rotation, a transient dipole moment may be induced
and a rotational spectrum observed. The intensity of the rotational spectrum is
proportional to the square of the dipole moment, and so highly polar molecules such as
HCl display strong absorptions in the microwave. Microwave spectroscopy finds several
uses. Microwave ovens operate on the rotational excitation of water molecules in food.
Water is a polar molecule and can absorb microwave radiation, making the water
molecules rotate faster and transfer heat to neighbouring molecules. Radar systems also
use microwave radiation. very little loss of signal occurs in transmission because most of
the molecules in the air: nitrogen, oxygen and carbon dioxide are microwave inactive.

Vibrational spectroscopy

In this case, the gross selection rule is that there must be a change in the dipole moment
of the molecule during a vibration for the vibration to be infrared active. Since
homonuclear molecules do not possess a permanent dipole moment and there is no
change in the dipole moment when the molecule vibrates, they are also infrared inactive.
Heteronuclear diatomic molecules like HCl are IR active. However, some of the
vibrations of molecules like carbon dioxide, which possess no dipole moment are infrared
active. Carbon dioxide has three modes of vibration (Fig. 1).

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 5 (TRANSITION PROBABILITIES AND
TRANSITION DIPOLE MOMENT. OVERVIEW OF
SELECTION RULES)
____________________________________________________________________________________________________

Figure 1 Vibrational modes of carbon dioxide

In the first mode, the two CO bonds compress or expand in phase, so that the net dipole
moment remains zero. In the second, bending, mode, the molecule becomes bent like
water and acquires a dipole moment. This motion is hence infrared active.

In the third mode, asymmetric stretch, one CO bond compresses while the other stretches,
leading to an asymmetric distribution of charge and a net dipole moment. This vibration
is also infrared active.

Raman spectroscopy

Vibrations are also observed using Raman spectroscopy. The mechanism of interaction
with the electromagnetic radiation is different in this case and is based on the scattering
of radiation. The electric field induces a dipole moment in the molecule. The molecular
property that must change for a rotation or vibration to be Raman active is the
polarizability, which measures the extent to which the electron distribution of a molecule
can be disturbed by an electric field. Thus it is not necessary that a molecule possess a
dipole moment for it to be Raman active. Homonuclear diatomic molecule like hydrogen,
CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)
MODULE No. : 5 (TRANSITION PROBABILITIES AND
TRANSITION DIPOLE MOMENT. OVERVIEW OF
SELECTION RULES)
____________________________________________________________________________________________________

nitrogen, etc. also display rotational Raman spectra, because they have anisotropic
polarizabilities – it is easier to induce a dipole moment along their bond axis than in other
directions. In other words, they are more polarizable along the bond axis. When these
molecules rotate, their polarizability changes in shape. However, spherically symmetrical
molecules like methane are rotational Raman inactive.

Homonuclear diatomic molecules also show vibrational Raman spectroscopy. The

symmetric stretch vibration of carbon dioxide (Fig. 1) is not infrared active, but it is
Raman active, as the polarizability increases when the molecule is stretched and
decreases when it is compressed.

Electronic spectroscopy

For homonuclear diatomic molecules, there are certain selection rules that can be easily
deduced. The first is the Laporte selection rule derived above, according to which the
parity of the wave function must change during a transition.

If the Hamiltonian of a system is spin-independent, the system cannot change its spin
angular momentum during a transition. We thus have the ΔS = 0 selection rule.

It must also be emphasized that these rules apply to electric dipole transitions only. The
radiation also has a magnetic field, and magnetic dipole transitions may also be induced.
However, they are much weaker than electric dipole transitions, and are only of
importance when the selection rules do not permit electric dipole transitions. The reason
is that the magnetic field (B) is much weaker than the electric field (E = cB) since the
value of the speed of light (c) is very large. Higher order (electric quadrupole) moments
may also contribute to the transition.

Certain forbidden transitions (such as n → π*) are also observed, although with very low
intensities. Some other mechanisms (vibronic coupling. i.e. coupling of electronic and
vibrational wave functions) allow these transitions to take place. Similarly, the spin
selection rule is also frequently violated,

5. Summary

• The probability of a transition is proportional to the square of the transition dipole

moment.
• The transition dipole moment is the transient dipole moment induced in the molecule
during a transition.
• It involves an integral of a triple product of the excited state wave function, the dipole
moment operator and the ground state wave function.

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 5 (TRANSITION PROBABILITIES AND
TRANSITION DIPOLE MOMENT. OVERVIEW OF
SELECTION RULES)
____________________________________________________________________________________________________

• Though a difficult quantity to evaluate, often it is enough to know the symmetry

properties of the three quantities in the triple product to predict the selection rules.
• Transitions between levels of same symmetry are laporte forbidden

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 5 (TRANSITION PROBABILITIES AND
TRANSITION DIPOLE MOMENT. OVERVIEW OF
SELECTION RULES)