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:MOLECULAR SPECTRA:

Introduction to molecular spectra:

Apart from the ground state, a molecule can be in a higher energy state, and transitions between
the various energy levels give rise to the observed molecular spectra. The energy of a diatomic
molecule arises from three modes:
(i) the electronic configuration of the electrons in the molecule,
(ii) the vibration of the atoms about the equilibrium position, and
(iii) the rotation of the molecule as a whole about its centre of mass.
The total energy of a molecule can be expressed as the sum of three independent terms:
E = Ee+ Ev + Er ...(1)
Ee , Ev , Er are quantised and Ev > Er .
If the molecule remains in its ground state level of electronic and vibrational energies, and if it
suffers transitions between different rotational energies, we get the pure rotational spectrum of
the molecule.
These spectra are in the microwave and far infrared regions. If the molecule remains in its
ground state level of electronic energy, and if transitions occur between different vibrational and
rotational energies we get the vibration-rotation spectrum of the molecule.
These spectra are in the near infrared region. If transitions occur between different electronic-
vibrational-rotational energy levels, we get the electronic spectrum of the molecule. These
spectra are in the visible and ultraviolet regions.
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Theory of the origin of pure rotational spectrum of a molecule

 Consider a diatomic molecule as consisting of atoms of masses �1 and �2 a distance R

apart. The diatomic molecule can rotate about its centre of mass as shown in Fig
 The moment of inertia of this molecule about an axis passing through its centre of mass
and perpendicular to a line joining the atoms is
� = �1 �21 + �2 �22 ………..(1)

where �1 and �2 are the distances of �1 and �2 , respectively from the centre of mass.
From the definition of centre of mass
�1 �1 = �2 �2 …..(2)
� = �1 + �2 …….(3)
From equation (2) and (3)
� �
�1 = � +2� R and �2 = � +1� R
1 2 1 2

Substituting these values of �1 and �2 in equation (1)

�1 �2 2 �2 �1 2 �1 �2
� = (� 2 �2 + (� 2 �2 = �2
1 + �2 ) 1 + �2 ) �1+ �2

Or

� = �' �2 …….(4)

Here the reduced mass �' is defined as

� �
�' = � 1+ �2 ……(5)
1 2

The angular momentum L of the molecule has the magnitude L = ��

The angular momentum of the rotating diatomic molecule is quantised according to

�= �(� + 1)ℏ……(6) J= 0.1,2,3….

J is called the rotational quantum number.

1
The rotational kinetic energy of a diatomic molecule is �� = 2 ��2
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1 �2 �(�+1)ℏ2
∴ �� = 2 ��2 = 2�
= 2�
………(7)

Rotational transitions occur only in those molecules which possess a permanent electric dipole
moment.
For this reason nonpolar diatomic molecules such as �2 and symmetric polyatomic molecules
such as ��2 and ��4 do not exhibit rotational spectra.
The selection rule for rotational transitions is �� = ± 1 ...(8)

Rotational spectra are always obtained in absorption.

Hence for a transition from some initial state of quantum number J to the next higher state of
quantum number J + 1, the frequency of the absorbed photon is
∆� ��+1 − �� ℏ
��→�+1 = = = 2��(J+1)………(9)
ℏ ℏ

The spectrum of a rigid molecule therefore consists of equally spaced lines

 Importance of the pure rotational spectrum for determining the properties of a molecule:
The frequency difference between two successive lines in the pure rotational spectrum of
a diatomic molecule is given by
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ℏ
∆� = ��+1→�+2 − ��→�+1 = 2��
By measuring ∆�, the moment of inertia I of the molecule can be calculated. Now,
� �
� = �' �2 = � 1+ �2 �2
1 2

Thus the distance R between the nuclei can be calculated. This gives the length of the
chemical bond between the atoms.
Theory of the origin of the vibration – rotation spectrum of a diatomic molecule
When sufficiently excited, a molecule can vibrate as well as rotate. We shall consider only
diatomic molecules.
The below fig shows the how potential energy of a diatomic molecule varies with inter atomic
distance R.

� = − � � − �°
shape of the curve is very nearly a parabola.In this region, then.
1
� = �° + (� − �° )2 ……..(1)
2

where �° is the equilibrium separation of the atoms. The inter atomic force that gives rise to this
potential energy
��
� =− �� =− �(� − �° )…….(2)
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On integrating the above equation

�� = �( � − �° )

1
V=2 �(� − �° )2

The force is just the restoring force that a stretched or compressed spring exerts and, as with a
spring, a molecule suitably excited can undergo simple harmonic oscillations.
Classically, the frequency of a vibrating body of mass m connected to a spring of force constant
k is

( from Newton’s law of motion

� = ��
d2 x
F= -kx � = m' dt2

On equating both equation

d2 x −��
=
dt2 m'

d2 x −��
+ ' =0
dt2 m
d2 x
+ ω2 x = 0
dt2
Where
k
ω2 =
m'
� = 2��

1 k
Then � = 2� m'
)

1 k
�° =
2π m
……(3)

In the diatomic molecule we have two bodies of masses m1 and m2 joined by a spring.
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The use of the “reduced mass” reduces the problem of two particles m1 and m2 vibrating about
their common centre of mass to the problem of a single mass m′ vibrating about a fixed point
(below fig).
The frequency of oscillation of such a two-body oscillator is

1 k
�° =
2π m'
………….(4)

When the harmonic oscillator problem is solved quantum mechanically, the energy of the
oscillator is found to be restricted to the values
�2� 2� 1 2
( ��2 + ℏ2
� − � � − �°
2
� = 0)

1
�� = � + ℎ�° ………….(5)
2

Here v is the vibrational quantum number. It may have the values v = 0, 1, 2, 3, ... Substituting
the value of �° from Eq. (4)

1 1 k h
�� = � + 2 ℎ
2π m'
where ℏ = 2π
1 k
�� = � + 2 ℏ m'
…………….(6) eigen expression for vibrational energy

These levels are sketched on Fig. 19.13. For large-amplitude vibrations, the parabola does not fit
the actual energy curve. Eq. (6) no longer holds.
The energy well is wider than the parabola for the higher �� ’s, and therefore these energy levels
are closer together than the lower�� ’s.
This diagram also shows the fine structure in the vibrational levels caused by the simultaneous
excitation of rotational levels.
The selection rule for transitions between vibrational states is
∆� = ±1 …………(7)
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(Pure vibrational spectra are observed only in liquids. This is because interactions between
neighbouring molecules prevent their rotational motion. The vibrations and rotations of a
molecule take place independently of each other).
Under these circumstances the energy levels of a diatomic molecule are specified by

1 k �(�+1)ℏ2
��,� = �� = � + 2 ℏ m'
+ 2�
.........(8)

�� is very much larger than �� . Even at high temperatures only the vibrational states
corresponding to v = 0 and v = 1 are excited.
Below fig shows the J = 0, 1, 2, 3 and 4 levels of a diatomic molecule for the v = 0 and v = 1
vibrational states.

It also shows the spectral lines in absorption. The selection rules are ∆� = 1 and ∆� = ±1. The
transition with ∆� = 0 is not allowed.

The v = 0 → v = 1 transitions fall into two categories :

(i) P Branch: Here, ∆J = – 1 (i.e., J → J – 1).
From Eq. (8) the frequencies of the spectral lines in the P branch are given by

�1,�−1 − �0,� 1 k ℏ
�� = = '
+ J + 1 J − J(J + 1)
ℎ 2π m 4πI

Or
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ℏ
�� = �� + (� + 1) 2πI
…….(9) J=1,2,3…….

(ii) R Branch: Here, ∆J = +1 (i.e., J → J + 1)

�1,�−1 − �0,� 1 k ℏ
�� = = '
+ J + 1 J + 2 − J(J + 1)
ℎ 2π m 4πI

Or
ℏ
�� = �� + (� + 1)
2πI
………..(10) J=1,2,3……

There is no line at v = �� (the Q branch) because transitions for which ΔJ = 0 are forbidden in
diatomic molecules.
ℏ
The spacing between the lines in both the P and the R branch is � = 2�� Hence, by measuring
the frequencies of these lines, the moment of inertia of the molecule and the length of the
chemical bond can be calculated.
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Electronic Spectra of Molecules:

 The electronic spectra of molecules arise when the electrons of a molecule are excited to
higher energy states. The energy involved in this process is generally large.
 Therefore, the electronic spectra of molecules are usually found in visible and ultraviolet
region. Thus electronic spectra arise due to the changes in the arrangement of molecular
electrons. The molecule is characterised by a discrete set of electronic energy states.
We can write the total energy E of a molecule
� = �� + �� + �� …. ...(1)

where Ee is the energy associated with the electronic exciation, and Ev and Ej are the vibrational
and rotational energies.
In a transition, the total energy change is the sum
∆� = ∆�� + ∆�� + ∆�� , where ∆�� , ∆�� ��� ∆�� represent the changes in the electronic,
vibrational, and rotational energies respectively.
(These are of the order of ∆ Ee ∼ 1 eV, ∆ Ev ∼ 0.1 eV ∆ Ej ∼ 0.001 eV. For a given electronic
transition, the spectrum consists of many lines arising due to the energy changes ∆ Ev and ∆ Ej .)

 These lines are so close to each other in frequency that the spectrum looks like a band.
Consider the vibrational structure of a band due to a transition between electronic states
Fe2 and Fe1 .
 The probability of transition between two given vibrational levels of two electronic
states is determined by Franck Condon principle.
 According to FranckCondon principle, the transition between different vibrational
states should be represented by vertical lines. This is due to the fact that electrons move
and rearrange themselves much faster than the nuclei of molecules.

Fig 1
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 For example, the time for an electron to circle a hydrogen nucleus is of the order of
10−16 s, which is thousand times less than the typical period of vibration 10−13 s of the
molecule.
 Thus the internuclear distance (R) of a vibrating molecule does not change appreciably
in course of transition between two electronic states.
 Hence the transition should be represented by a vertical line, that is a line of constant R.
Secondly, the Franck-Condon principle states that transitions from one state to another
are most probable when nuclei are in their mean positions i.e., observed transitions
between two states should start from extreme positions of vibrational level.
 This is due to the fact that nuclei spend longest time at mean positions as the vibrational
kinetic energy is zero there.
 Above Fig1. shows the potential energy of the molecules as a function of internuclear
distance for two electronic energies Fe1 and Fe2 with vibrational energy levels.
 Quantum mechanics predicts that most probable position of the nuclei for the lowest
vibrational energy (v2 = 0) is the equilibrium position i.e., mid-position. However, the
most probable internuclear distance for vibrational levels other than v2 = 0, corresponds
to the extreme positions. Thus the transitions start from extreme positions for levels
other than v2 = 0.
 As the equilibrium values of internuclear distances in a molecule will be different in
different electronic states, the vibrational frequencies will be different in different states.
 Again considering the fact that the vibrations of the molecule are not simple harmonic,
i.e., vibrations are anharmonic vibrations, the lines get crowded towards the high
frequency end of the spectrum.
The electronic emission spectrum of a molecule due to vibration is shown in Fig. 2

fig.2
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 [Each of these lines is spread out into a band due to transitions between different
rotational energy levels. The bands in a band system are grouped together into different
progressions.
 Each progression consists of the set of bands which arise from transitions from a fixed
initial vibrational energy level to different final Fig1 Fig.2 vibrational levels. In Fig.2,
zero and one progressions are shown.
 If the progression obtained by transitions from vibrational energy in upper electronic
state to different vibrational energy levels in lower electronic state are considered, we
find that the progression ends in a continuum. This continuum arises due to dissociation
of the molecule.
 Now we consider the rotational lines in each band. These lines are again not equally
spaced due to the fact that moments of inertia of molecules are different in different
electronic states.
 Thus the lines in a band get crowded towards one end. The intensity also shows an
abrupt change.
 There are no selection rules governing the changes between vibrational energy levels.
The transitions between rotational energy levels obey the selection rule ∆ J = – 1, 0 or +
1 with additional requirement that transition with J = 0 to another level with J = 0 is not
allowed.
 In this case, we get three branches of lines in any given band namely the R-branch, Q-
branch and P-branch ( below Fig.)]
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Fluorescence and Phosphorescence

 Molecules which absorb radiation in the near ultraviolet and visible range may re-emit it
at a longer wavelength. This phenomenon is called fluorescence and is illustrated in Fig.

 First, absorption transitions occur from a lower electronic state to some vibrational levels
of an upper electronic state. The absorption transitions are governed by the Franck-
Condon principle.
 For example, have shown in above Fig. a transition leading from the lowest vibrational
level of the ground electronic state of the molecule to an excited vibrational level of an
upper electronic state.
 The molecule may then lose vibrational energy through collisions with other molecules
(thermal decay) and reach the lowest vibrational state v′ = 0 of the excited electronic
level.
 This process is often more rapid than spontaneous emission of radiation, so that when the
molecule finally re-emits radiation, it is from the vibrational level v′ = 0. Fluorescent
radiation is, therefore, of lower frequency than that of the absorbed radiation.
 Fluorescence excited by ultraviolet light has many applications, for instance to help
identify minerals and biochemical compounds.This principle is applied in fluorescent
lamp.
 The fluorescence phenomenon involves a spontaneous emission between two electronic
states of the same multiplicity.
 But phosphorescence phenomenon involves the spontaneous emission from an excited
electronic state to a lower one of different multiplicity.
 For example, let us assume that a molecule first undergoes an absorption transition from
a singlet ground state 1 X to a singlet excited state 1 A (Fig.).
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 Thermal degradation of the vibrational energy then occurs via collisions with other
molecules.
 Suppose now that the state 1A is coupled to a triplet state 3A of similar energy.
 Instead of going down the vibrational ladder of the state 1A, the
 molecule then undergo an intersystem crossing and be transferred by a radiationless
transition into the triplet state 3A. After the crossing has occurred, thermal decay will
proceed within the 3A well, until the molecule has reached the lowest vibrational level of
the 3A state. This triplet state may now decay to the ground (singlet) state 1X by a
radiative transition called phosphorescent emission. Indeed, although electric dipole
transitions between the excited 3A state and the ground state 1X are spin-forbidden
because of the selection rule ∆S = 0, radiative transitions 3A → 1X may not be absolutely
forbidden, and may occur slowly through spin -orbit interactions.
 Such transitions accordingly have long half-lives, and the resulting phosphorescent
radiation may be emitted minutes or even hours after the initial absorption.