Spectra of Diatomic Molecules

DIATOMIC MOLECULE
A molecule having two atoms separated by a distance which is large as compared to atomic dimension is called
a diatomic molecule.
Examples Hf Of Nf CO, NO etc.

Diatomic molecules can be classified as follows:

Homonuclear molecule. It consists of two identical atoms i.e the molecule has two identical nuclei.
Examples. H, O, N; etc
Metro-nuclear molecule. It consists of two dissimilar atoms i.e the molecule has two non-identical nuclei.
Examples SO. HCl. CO etc

Molecular Spectra:
Molecules can remain in the ground state as well as in excited states. The transition between the allowed energy
states of a molecule with the emission or absorption of radiation i.e. photon, gives rise to molecular spectra.
𝐸𝑖 −𝐸𝑓
The frequency of the emitted or absorbed photon is 𝛾 =
ℎ
The cause of excitation could be due to
i) Energy due to Rotation of the molecule Er
ii) Energy due to Vibration of the molecule EV
iii) Energy due to Excitation of the electrons in the molecule Ee

Therefore, the total energy of the molecule is E= Er + EV + Ee

Molecular spectra generally fall into three distinct regions of wavelength.

1. Pure Rotational spectrum. The transition between the rotational energy states of a molecule with the
emission or absorption of a photon gives rise to pure rotational spectrum,
In this case the electronic configuration of the atoms and the vibrational state of the molecule remain the
same Rotational levels are separated by quite small energy intervals of the order of 10-3 eV and pure rotation
spectra lie in the microwave or far infra red region (107 Ao).
2. Rotational-vibrational spectrum. The transition between the vibrational energy states of a molecule
with the emission or absorption of a photon, when the electronic configuration of the atoms remains
the same, gives rise to rotational vibrational spectrum.
If the rotational states of the molecule also do not change, we get a pure vibrational spectrum which lies lies
in the near infrared region (1 05 Ao). The vibrational states are separated by energy intervals of about 0.1 eV.
3. Electronic spectrum. The transition between two electronic energy states of an atom in a molecule
with emission or absorption of photon gives rise to electronic spectrum. The energy separation
between different electronic states is 1 eV - 10 eV and the electronic spectra lies in the visible and
ultraviolet part of the spectrum.

The electronic energy levels in a molecule are separated by energy intervals of the order of 1 eV - 10 eV. Each
electronic energy level may have a number of vibrational energy levels which are separated by energy intervals
of about 0.1 eV. Each vibrational energy level may have a number of rotational energy levels separated by
energy intervals of the order of 10-3 eV.
Thus, each electronic energy level in reality consists of a large number of levels closely spaced together. The
transition between different electronic energy levels each of which is a band of a number of levels gives rise to
band spectrum rather than line spectrum.
ROTATIONAL SPECTRA
Consider a diatomic molecule of masses m1 and m2
Which are at distances of r1 and r2 from the center of
mass respectively and the masses rotate about the
center of mass with angular velocity 𝜔

Let R= r1 + r2 --------(1)

For the balanced system about the center of mass

𝑚1 𝑟1 = 𝑚2 𝑟2 ----------(2)
The moment of Inertia of the diatomic molecule about an axis passing through the center of mass is given by
𝐼 = 𝑚1 𝑟12 + 𝑚2 𝑟22 ⋯ ⋯ (3)
From eq (2)

𝑚2
𝑟1 = 𝑟
𝑚1 2
𝑚2 𝑚1 +𝑚2
From eq (1) 𝑅 = 𝑟1 + 𝑟2 = 𝑟 + 𝑟2 = 𝑟1 ( )
𝑚1 2 𝑚1

𝑚1
Or 𝑟2 = (𝑚 )𝑅
1 +𝑚2
Similarly, we get
𝑚2
𝑟1 = ( )𝑅
𝑚1 + 𝑚2
Substitute the value of r1 and r2 in eq (3) gives

𝑚1 𝑚22 2
𝑚2 𝑚12
𝐼= 𝑅 + 𝑅2
(𝑚1 + 𝑚2 )2 (𝑚1 + 𝑚2 )2

𝑚1 + 𝑚2
= 𝑚1 𝑚2 𝑅2
(𝑚1 + 𝑚2 )2

𝑚 𝑚
= 𝑚 1+𝑚2 𝑅2
1 2

Therefore, I = µR2 ……(4)

The KE of rotation of the molecule is given by

1
𝐸 = 2 𝐼𝜔2 … . . (5)

The angular momentum L of the molecule about the axis of rotation is given by
𝐿 = 𝐼𝜔 … . . (6)
Using eq (4) and (6) in eq (5) gives
𝐿2
𝐸 = … … . (7)
2𝐼
Where, the orbital angular momentum is quantized and is given by 𝐿 = √𝐽(𝐽 + 1)ℏ. This J is the rotational
quantum number and takes integral values 0, 1, 2, 3…..
Eq (7) can be written in terms of J as
𝐿2
𝐸𝐽 =
2𝐼
ℏ2
𝐸𝐽 = 𝐽(𝐽 + 1) … … . (8)
2𝐼
 ℏ2
𝐸𝐽 = 𝐽(𝐽 + 1) … … . (9)
2µ𝑅2

Selection Rules: 𝛥𝐽 = ±1 and 𝐽 = 0, 1, 2, 3 … …

Suppose that the transition takes place from initial energy state Ei = EJ of quantum number J and final state Ef =
EJ-1 and quantum number J-1, then the frequency of the photon emitted is
ℎ𝛾 = 𝐸𝑖 − 𝐸𝑓
𝐸𝐽 − 𝐸𝐽−1
𝛾 =
ℎ

ℏ2 ℏ2
𝐽(𝐽+1) −(𝐽−1)𝐽
2𝐼 2𝐼
=
ℎ

𝐽ℏ2
= 2𝐼ℎ (𝐽 + 1 − 𝐽 + 1)

𝐽ℏ2
𝛾=
𝐼ℎ
or
𝐽ℎ
𝛾= = 𝐽𝛾𝑜 𝑤ℎ𝑒𝑟𝑒 𝐽 = 0, 1, 2, 3 … …
4𝜋 2 𝐼
or
ℎ
where, 𝛾𝑜 = 4𝜋2𝐼
Similarly, in going from initial state with quantum number J to final state with quantum number J+1 gives
𝐸𝑖 − 𝐸𝑓
𝛾=
ℎ
𝐸𝐽+1 − 𝐸𝐽
=
ℎ

ℎ(𝐽 + 1)
𝛾=
4𝜋 2 𝐼

From the energy level diagram, it is observed that the

Spacing between levels is not fixed but goes on
increasing with J values. However, the frequency lines
are equally spaced.

The energy levels for rotational spectrum are given by

ℏ2
𝐸𝐽 = 𝐽(𝐽 + 1) … … . (8)
2𝐼

And J=0, 1, 2,3 ……

*) For 𝐽 = 0 … … …. 𝐸𝐽 = 𝐸0 = 0

ℏ2
*) For 𝐽 = 1 … … …. 𝐸𝐽 = 𝐸1 = 2
2𝐼

ℏ2
*) For 𝐽 = 2 … … …. 𝐸𝐽 = 𝐸2 = 6
2𝐼

ℏ2
*) For 𝐽 = 3 … … …. 𝐸𝐽 = 𝐸3 = 12 2𝐼
 ℏ2
*) For 𝐽 = 4 … … …. 𝐸𝐽 = 𝐸4 = 20 2𝐼

And
2ℏ2
𝐸1 − 𝐸0 = ,
2𝐼
4ℏ2
𝐸2 − 𝐸1 = 2𝐼
,
6ℏ2
𝐸3 − 𝐸2 = ,
2𝐼
8ℏ2
𝐸4 − 𝐸3 = 2𝐼
,…….,
This shows that the energy levels are not fixed but go on increasing.

To show that the frequency lines are equally spaced:

We know that
𝐽ℎ
𝛾= 2 = 𝐽𝛾𝑜 𝑤ℎ𝑒𝑟𝑒 𝐽 = 0, 1, 2, 3 … …
4𝜋 𝐼
ℎ
and 𝛾𝑜 = 4𝜋2𝐼

*) For J = 0, 𝛾 = 𝐽𝛾𝑜 = 0𝛾𝑜 = 0 → THUS FOR J =0 (GROUND STATE), 𝛾 = 0𝛾𝑜 = 0, the molecule DOES NOT
ROTATE
*) For J = 1, 𝛾0 = 𝛾𝑜
*) For J = 2, 𝛾1 = 2𝛾𝑜
*) For J = 3, 𝛾2 = 3𝛾𝑜
*) For J = 4, 𝛾3 = 4𝛾𝑜
……….
Therefore,
𝛾1 − 𝛾0 = 𝛾𝑜 ,
𝛾2 − 𝛾1 = 𝛾𝑜 ,
𝛾3 − 𝛾2 = 𝛾𝑜 ,
ℎ
……….. This shows that the frequency lines are equally spaced and the spacing is multiples of 𝛾𝑜 =
4𝜋2 𝐼

The rotational energy levels are very small and separated by energy of the order of 10-3 eV. The energy levels
lie in the microwave or infrared region(10-7 Ao).

Problem: The J =0 to J =1 absorption line of CO occurs at a frequency of 1.153x1011 Hz. Calculate the MI, bond
length and lowest energy level of the molecule. Given 1 amu = 1.66x10-27Kg.
Solution:
For J → J+1, the frequency
𝐽ℎ (𝐽 + 1)ℎ
𝛾 = 2 𝑓𝑜𝑟 𝑠𝑡𝑎𝑡𝑒 𝐽 𝑎𝑛𝑑 𝛾 = 𝑓𝑜𝑟 𝑠𝑡𝑎𝑡𝑒 (𝐽 + 1)
4𝜋 𝐼 4𝜋 2 𝐼

(𝐽+1)ℎ 𝐽ℎ ℎ
Thus 𝛾= − =
4𝜋2 𝐼 4𝜋2 𝐼 4𝜋2 𝐼

(𝐽+1)ℎ ℎ
Or we may substitute J=0 and J=1 in 𝛾 = to get above formula 𝛾 =
4𝜋2 𝐼 4𝜋 2 𝐼

ℎ 6.63∗10−34
MI for Co molecule: 𝐼 = 4𝜋2 𝛾 = = 1.46 ∗ 10−46 𝑘𝑔 − 𝑚2
4𝜋2 ∗1.153∗1011

Now, I = µR2
 𝑚 𝑚
= 𝑚 1+𝑚2 𝑅2
1 2
16 𝑥 12
= 16+12
𝑥 1.66 ∗ 10−27 𝑅2 = 1.14 ∗ 10−26 𝑅2
Therefore,
𝐼 1.46∗10−46
Bond length: 𝑅=√ = √ = 1.14 ∗ 10−10 𝑚
µ 1.14∗10−26

Energy: the lowest energy level corresponds to J=1

ℏ2 ℏ2 ℎ2
𝐸𝐽 = 𝐽(𝐽 + 1) =2 =
2𝐼 2𝐼 4 𝜋2𝐼

6.63 ∗ 10−34 ∗ 6.63 ∗ 10−34

𝐸𝐽 = = 7.61 ∗ 10−23 𝐽 = 4.76 ∗ 10−4 𝑒𝑉
4 𝜋 2 ∗ 1.46 ∗ 10−46

Problem: Find the energy and angular velocity of CO molecule in the ground state. Given bond length of CO
molecule= 0.113nm, mC = 1.99 ∗ 10−26 𝑘𝑔 𝑎𝑛𝑑 mO = 2.66 ∗ 10−26 𝑘𝑔
Solution: For the ground state J=0
ℏ2
Therefore, energy 𝐸𝐽 = 𝐽(𝐽 + 1) 2𝐼 = 0
Angular velocity:
1
Since 𝐸 = 2 𝐼𝜔2
we have 𝜔 = √2𝐸/𝐼 = 0

Problem: Calculate the rotational energy corresponding to J =1 for hydrogen molecule, given that inter-
molecular distance (bond length) is 0.074 nm and mass of H atom is 1.674 x 10 -27 kg (Given h = 6.63 x 10-34 JS.)

Solution. Mass of each hydrogen atom m = 1.674 x 10 2 kg

𝒎 𝟏 𝒎𝟐 𝒎𝟐 𝒎
Reduced mass for H atom µ = = = = 𝟎. 837 ∗ 10−27 𝑘𝑔
𝒎𝟏 +𝒎𝟐 𝟐𝒎 𝟐
Inter molecular distance = bond length R = 0.074 nm = = 0.074 x 10-9 m

Moment of Inertia I=MR2= 0.837 ∗ 10−27*0.074 x 10-9 * 0.074 x 10-9 = 𝟒. 𝟓𝟖 ∗ 10−48 kg-m2

Now for J =1,

ℏ2 ℏ2 ℎ2
𝐸𝐽 = 𝐽(𝐽 + 1) = 2 =
2𝐼 2𝐼 4 𝜋2𝐼

6.63 ∗ 10−34 ∗ 6.63 ∗ 10−34 −20

0.243 ∗ 10−20
𝐸𝐽 = = 0.243 ∗ 10 𝐽 = = 0.152𝑒𝑉
4 𝜋 2 ∗ 𝟒. 𝟓𝟖 ∗ 10−48 1.6 ∗ 10−19

VIBRATIONAL SPECTRA

Vibrations of a molecule. We assume that the inter-nuclear distance remains constant i.e. the diatomic
molecule behaves as a rigid body.
But on being sufficiently excited, the nuclei do not maintain a constant fixed separation. They oscillate back
and forth along the line joining them in such a way that the center of mass remains fixed. The vibratory motion
is in addition to the rotation of the molecule.
Expression for vibrational energy levels
Consider two atoms forming the molecule have masses m1 and m2 , and are separated by an equilibrium
distance Ro between them. As the molecule vibrates along the line joining the atoms the distance between
them changes. Let x be the extension of the spring.
Then, Ro + x = (x2 – x1 )

x = (x2 – x1 ) - Ro -------(1)

The extension x → +ve when spring is stretched

x → -ve when spring is compressed

Thus, we have,
F1 = + kx ------(2) for mass m1
and F 2 = - kx ------(3) for mass m2
where k is called the force constant and is a measure of the stiffness of the bond.

From eq (2) and (3) we get

𝑑 2 𝑥1
F1 = m1 = +kx ------------(4)
𝑑𝑡 2

𝑑 2 𝑥2
F2 = m2 𝑑𝑡 2
= -kx ------------(5)

Multiply eq(4) by m2 and eq (5) by m1 and subtracting eq 5 from eq 4 gives

𝑑 2 𝑥1 𝑑 2 𝑥2
m2 m1 - m1m2 = - m1kx - m2 kx
𝑑𝑡 2 𝑑𝑡 2

𝑑 2 (𝑥2 −𝑥1 )
m1 m2 𝑑𝑡 2
= -k(𝑚1 + 𝑚2 )x ---------(6)

𝒎𝟏 𝒎𝟐 𝑑 2 (𝑥2 −𝑥1 )
or 𝒎𝟏 +𝒎𝟐 𝑑𝑡 2
=-kx

𝑑 2𝑥 𝑑𝑅𝑜
or µ 𝑑𝑡 2
=-kx using eq (1)and since R o is a constant, 𝑑𝑡
=0

This shows that the molecule system behaves like reduced mass system, we have
𝑑 2𝑥 𝑘 𝒎𝟏 𝒎𝟐
= - x -----(7) where µ=
𝑑𝑡 2 µ 𝒎𝟏 +𝒎𝟐

1 𝑘
Eq (7) represents a SHM and the solution is 𝛾𝑜 = 2𝜋
õ --------------(8)

Since F= -kx
From the quantum mechanical point of view, where V is the PE of the molecule
𝑑𝑉
F=- = -kx
𝑑𝑥
This gives, 𝑑𝑉 = 𝑘𝑥 𝑑𝑥
 𝑥 1
Or 𝑉 = ∫0 𝑘𝑥 𝑑𝑥 = 𝑘𝑥 2
2
Now, Schrodinger eq given by
ℏ2 𝑑 2 𝜓
+ (𝐸 − 𝑉)𝜓 = 0
2𝑚 𝑑𝑡 2
1
Substituting 𝑉 = 𝑘𝑥 2 and m= µ in above equation gives
2

ℏ2 𝑑 2 𝜓 1
− 2µ 𝑑𝑡 2 + 2 𝑘𝑥 2 𝜓 = 𝐸𝜓 -----------(9)

Solving eq 9 gives the energy levels of a simple harmonic oscillator :

1
𝐸𝑉 = (𝑣 + ) ℎ𝛾𝑜 --------------(10)
2

1 1 𝑘
𝐸𝑉 = (𝑣 + ) ℎ√ ----------------(11) using eq 8
2𝜋 2 µ

Where, 𝑣 = 0, 1, 2, 3 ….. is the vibrational quantum number.

Eq (11) shows that the vibrational energy levels are equally spaced.

1 1 1
➢ For 𝑣 = 0 (ground state) 𝐸0 = (𝑣 + 2) ℎ𝛾𝑜 = (0 + 2) ℎ𝛾𝑜 = 2
ℎ𝛾𝑜
3
➢ For 𝑣 = 1, 𝐸1 = 2 ℎ𝛾𝑜
5
➢ For 𝑣 = 2, 𝐸2 = 2 ℎ𝛾𝑜
7
➢ For 𝑣 = 3, 𝐸3 = ℎ𝛾𝑜
2
➢ ……….
Therefore, 𝐸1 − 𝐸0 = 𝐸2 − 𝐸1 = 𝐸3 − 𝐸2 = ℎ𝛾𝑜 → This shows that the vibrational energy levels are equally
spaced with spacing ℎ𝛾𝑜 .

Selection Rules :.
Only those transitions are allowed between vibrational energy levels for which the vibrational quantum number
v changes by one unit i.e.
Δ 𝑣 = + 1 and 𝑣 = 0, 1, 2, 3 …..

Frequency of lines in vibrational spectra.

If the transition occurs from an energy level with quantum number (v+ 1) to an energy level with quantum
number v, then
hγ = 𝐸𝑣+1 − 𝐸𝑣

1 1
Or hγ = (𝑣 + 1 + ) ℎ𝛾𝑜 − (𝑣 + ) ℎ𝛾𝑜
2 2
= ℎ𝛾𝑜

1 𝑘
Or γ= 𝛾𝑜 = √µ
2𝜋

This gives the frequency 𝛾𝑜 of spectral line in vibrational emission spectra. Similarly, the frequency of spectral
line in vibrational absorption spectra is also 𝛾𝑜 . Thus, we find that the frequency of radiation emitted (or
absorbed) is equal to classical frequency v0 irrespective of the values of vibrational quantum number.
Vibrational spectra lies in infra red region (from 8000Ao — 50,000Ao ) for a number of molecules.

Problem: Calculate the vibrational wavelength of HCl molecule. Given k = 470 N/m. 1 amu= 1.67x 10-27
𝑚 𝑚 1∗35
Solution: µ= 1 2 = x 1.67x 10-27 = 1.62 x 10-27 kg
𝑚1 +𝑚2 1+35

1 𝑘 1 470
Now frequency, γ = 2𝜋 √ µ = 2𝜋 √1.62 x 10−27 =8.6 x 1013 sec-1
 𝑐 3𝑥108
Therefore, wavelength λ = 𝛾 = 8.6 x 1013= 0.35 x 108 m= 35000 Ao This in in the IR region,

Problem: The force constant of CO molecule is 187 N/m. Find the frequency of vibration of CO molecule and
spacing between vibrational levels. Mass of 12C atom= 1.99 * 10-26kg , and 16O atom=2.66 x 10-26 kg.

Solution:
𝑚 𝑚 1.99 𝑥10−26 𝑥 2.66𝑥10−26
Reduced mass of CO molecule : µ= 𝑚 1+𝑚2 = 1.99 𝑥10−26+ 2.66𝑥10−26 = 1.14 𝑥10−26 𝑘𝑔
1 2

1 𝑘 1 187
Frequency of vibration : γ = 2𝜋 √ µ = 2𝜋 √1.14 𝑥10−26 = 2.04 x 1013 sec-1

Separation between vibrational energy levels of CO:

1 𝑘
𝐸𝑣+1 − 𝐸𝑣 = ℎ𝛾𝑜 = ℎ 2𝜋
õ

= 6.63 x 10−34 ∗ 2.04 x 1013

1.35 x 10−20 𝐽 = 8.44 𝑥 10−2 𝑒𝑉

VIBRATIONAL ROTATIONAL SPECTRA

Pure vibrational spectra are observed only in liquids in which no rotation can take place due to interaction
between adjacent molecules. Since the excitation energies involved in molecular rotation are much smaller
than those involved in vibration, the freely moving molecules in a gas or vapour are almost always rotating,
regardless of their vibrational states. The spectra of such molecules do not show isolated lines corresponding
to each vibrational transition, but instead a large number of closely spaced lines due to transitions between
various rotational states of one vibrational level and the rotational states of the other vibrational level. These
lines appear as broad streaks called vibration-rotation band.

The potential energy V versus inter-nuclear distance R

curve, we find that in the neighborhood of the
minimum of the curve, which corresponds to the
normal configuration of the molecule, the shape of the
curve is very nearly a parabola. Therefore, for lower
vibrational states of the molecule, the potential energy
curve is parabolic but for higher vibrational states i.e.
with increasing energy, the potential energy curve
deviates more and more from parabolic form, so that
the energy-well is wider than the parabola. As a result,
the spacing between adjacent energy levels of higher
vibrational quantum number is less than the spacing
between adjacent energy levels for lower values of
vibrational quantum number, so that for higher
quantum numbers, the energy levels are closer.

Vibration-rotation energy levels:

The vibration and rotation of a molecule can take place independently of each other.
Therefore, the total energy E of a molecule is the sum of the vibrational and rotational energy
Hence 𝐸𝑣,𝐽 = 𝐸𝑣 + 𝐸𝐽

1 ℏ2
𝐸𝑣,𝐽 =(𝑣 + ) ℎ𝛾𝑜 + 𝐽(𝐽 + 1) -------------(1)
2 2𝐼

1 ℏ2 1
➢ For 𝑣 = 0 𝑎𝑛𝑑 𝐽 = 0 : E0,0 =(0 + ) ℎ𝛾𝑜 + 0(0 + 1) = ℎ𝛾𝑜 → Ground State
2 2𝐼 2
1 ℏ2 1 ℏ2
➢ For 𝑣 = 0 𝑎𝑛𝑑 𝐽 = 1 : E0,1 =(0 + 2) ℎ𝛾𝑜 + 1(1 + 1) 2𝐼 = 2 ℎ𝛾𝑜 + 2 2𝐼
→ 1st excited state
1 ℏ2 1 ℏ2
➢ For 𝑣 = 0 𝑎𝑛𝑑 𝐽 = 2 : E0,2 =(0 + 2) ℎ𝛾𝑜 + 2(2 + 1) 2𝐼 = 2 ℎ𝛾𝑜 + 6 2𝐼
→ 2nd excited state
 1 ℏ2 1 ℏ2
➢ For 𝑣 = 0 𝑎𝑛𝑑 𝐽 = 3 : E0,3 =(0 + 2) ℎ𝛾𝑜 + 3(3 + 1) 2𝐼 = 2 ℎ𝛾𝑜 + 12 2𝐼
→ 3rd excited state
1 ℏ2 1 ℏ2
➢ For 𝑣 = 0 𝑎𝑛𝑑 𝐽 = 4 : E0,4 =(0 + 2) ℎ𝛾𝑜 + 2(2 + 1) 2𝐼 = 2 ℎ𝛾𝑜 + 6 2𝐼
→ 2nd excited state
Energy Level Diagram:

The energy level diagram is shown and corresponds to

𝑣 = 0 and 𝑣 = 1
J=0, 1, 2, 3, 4 ……..

Selection Rules:
Δ 𝑣 = + 1 and 𝑣 = 0, 1, 2, 3 … …
𝛥𝐽 = ±1 and 𝐽 = 0, 1, 2, 3 … …

J=0 → J=0 (𝑖𝑒 𝛥𝐽 = 0) transitions are not allowed.

Δ J= -1: transition lines correspond to the P branch

Δ J= 0 : No transitions → Q branch
Δ J= +1: transition lines correspond to the R branch

Δ 𝑣 = +1 corresponds to absorption spectra.

Δ 𝑣 = −1 corresponds to emission spectra.

Frequency of spectral lines:

We know that the total energy E of a molecule is the sum of the vibrational and rotational energy
ie. 𝐸𝑣,𝐽 = 𝐸𝑣 + 𝐸𝐽

1 ℏ2
𝐸𝑣,𝐽 =(𝑣 + 2) ℎ𝛾𝑜 + 𝐽(𝐽 + 1) 2𝐼 -------------(1)

(1) For P Branch:

We have 𝑣 = 0 → 𝑣 = 1 or Δ 𝑣 = +1
and 𝐽 → 𝐽 − 1 𝑜𝑟 𝛥𝐽 = −1

Energy of P lines:
ℎ𝛾𝑃 = 𝐸1,𝐽 − 𝐸0,𝐽−1
1 ℏ2 1 ℏ2
= [ (1 + ) ℎ𝛾𝑜 + 𝐽(𝐽 + 1) ] − [(0 + ) ℎ𝛾𝑜 + (𝐽 − 1)𝐽 ]
2 2𝐼 2 2𝐼
ℏ2
= ℎ𝛾𝑜 − 𝐽 𝐼
Therefore, the frequency of P lines

ℎ
𝛾𝑃 = 𝛾𝑜 − 𝐽 4𝜋2𝐼 with J= 1, 2, 3,……

(2) For R Branch:

We have 𝑣 = 0 → 𝑣 = 1 or Δ 𝑣 = +1
and 𝐽 → 𝐽 + 1 𝑜𝑟 𝛥𝐽 = +1

Energy of R lines: ℎ𝛾𝑅 = 𝐸1,𝐽+1 − 𝐸0,𝐽

1 ℏ2 1 ℏ2
= [ (1 + ) ℎ𝛾𝑜 + (𝐽 + 1)(𝐽 + 2) ] − [(0 + ) ℎ𝛾𝑜 + J(𝐽 + 1) ]
2 2𝐼 2 2𝐼
ℏ2
= ℎ𝛾𝑜 + (𝐽 + 1) 𝐼
Therefore, the frequency of R lines:

ℎ
𝛾𝑅 = 𝛾𝑜 + (𝐽 + 1) 4𝜋2𝐼 with J= 1, 2, 3,……
 (3) For Q branch
We have 𝑣 = 0 → 𝑣 = 1 or Δ 𝑣 = +1
and 𝐽 → 𝐽 𝑜𝑟 𝛥𝐽 = 0
Energy of Q lines: ℎ𝛾𝑄 = 𝐸1,𝐽 − 𝐸0,𝐽
1 ℏ2 1 ℏ2
= [ (1 + ) ℎ𝛾𝑜 + J(𝐽 + 1) ] − [(0 + ) ℎ𝛾𝑜 + J(𝐽 + 1) ]
2 2𝐼 2 2𝐼
= ℎ𝛾𝑜
Therefore, the frequency of R lines:
𝛾𝑄 = 𝛾𝑜

The transition for 𝛥𝐽 = 0 is not allowed and hence not observed in molecular spectra.

ℎ
The spacing between lines of P and R lines is 𝛥𝛾 = 4𝜋2 𝐼

ELECTRONIC SPECTRA OF DI-AND POLY ATOMIC MOLECULES

The energies of rotation and vibration in a molecule are due to the motion of the atomic nuclei, because the
whole mass of the molecule is concentrated in the nuclei.
In a molecule, the electrons can also be excited to higher energy states from their ground state. The spacing of
these levels is much greater than the spacing of vibrational or rotational levels. The electronic transitions thus
involve much greater energies and give rise to spectra in the visible or ultraviolet region.
Electronic energy levels in a molecule are separated by energies of the order of eV. Each electronic energy
level may have a number of vibrational energy levels, with each vibrational energy level further having a
number of rotational energy levels, with energy separation of 10-2: to l0-3 eV. Thus, each electronic level
consists of a large number of levels closely spaced together. Each electronic transition, therefore, produces a
series of closely spaced lines, called a band due to the presence of vibrational and rotational states in each
electronic state.

All molecules exhibit electronic spectrum, because a change in dipole moment is always accompanied by a
change in electronic configuration of the molecule. So, even homo-nuclear molecules like H 2 , N2 and O 2,
which do not exhibit either rotational or vibrational spectra because they do not possess a permanent dipole
moment do show electronic spectra which possesses rotational and vibrational line fine structure. The
moment of inertia and bond force constant of such molecules can be calculated from the line structure in
electronic spectral bands.

Frequency of electronic spectra:

When the electronic slates of a molecule arc excited, the total energy of the molecule in a given quantum
state, is given by
𝐸 = 𝐸𝐽 + 𝐸𝑉 + 𝐸𝑒
The frequency of radiation between any 2 electronic states is
𝐸 −𝐸 𝐸𝐽1 −𝐸𝐽2 𝐸 −𝐸 𝐸 −𝐸
𝛾 = 1ℎ 2 = ℎ
+ 𝑉1 ℎ 𝑉2 + 𝑒1 ℎ 𝑒2
or
𝛥𝐸 𝛥𝐸𝐽 𝛥𝐸𝑉 𝛥𝐸𝑒
𝛾= = + +
ℎ ℎ ℎ ℎ

This is most general type of transition and is known as rotation-vibration-electronic transition. Since Ee > EV > EJ , the
frequency or position of the electronic spectra is determined by ΔEe (i.e. change in Ee). This lies in the visible or ultraviolet
region.

SPECTRA OF HOMONUCLEAR DIATOMIC MOLECULE

The vibrational spectra are observed only in absorption. The electromagnetic radiation can induce transition
among vibrational energy levels. For transfer of radiation energy to vibrating molecule, an electrical coupling
should be present. If the vibrating molecule produces an oscillating dipole moment, then this dipole moment
interacts with electric field of radiation and thus gives rise to coupling. Molecules like HCl, HBr having
dissimilar atoms, have a resultant dipole moment which is a function of internuclear distance and therefore,
show vibrational spectra. Molecules like Hy Ny 0, which have similar atoms, do not possess net dipole moment.
Such molecules cannot interact with radiation and do not show vibrational spectra. This is why homonuclear
diatomic molecules do not show vibrational rotational spectra.

Problem: The carbon monoxide (CO) molecule has a bond length R of 0.113 nm and the masses of the
12C and 16O atoms are respectively 1.99 10-26 kg and 2.66 10-26 kg. Find (a) the energy
and (b) the angular velocity of the CO molecule when it is in its lowest rotational state.
Solution
(a) The reduced mass m of the CO molecule is

Problem: When CO is dissolved in liquid carbon tetrachloride, infrared radiation of frequency 6.42
1013 Hz is absorbed. Carbon tetrachloride by itself is transparent at this frequency, so the
absorption must be due to the CO. (a) What is the force constant of the bond in the CO molecule?
(b) What is the spacing between its vibrational energy levels?
Solution:

FRANK CONDON PRINCIPLE and FOTRAT DIAGRAMS

Electronic transitions take place so rapidly compared to time required for a vibrating molecule to complete a
cycle that we can consider that the internuclear distances in a molecule as unchanged while it takes place. This
is Frank Condon principle.

The Figure 1 below contains curves of potential energy versus internuclear distance for the electronic ground
state and first excited state in a diatomic molecule along with the vibrational energy levels for each state. The
probability density |ψ|2 in the various vibrational levels of each electronic state are also shown.
|ψ|2 is a maximum in the center of the range of motion for v = 0 level and a maximum at both ends of the
range of motion in the higher vibrational levels for v = 1, 2, 3,.....
Transitions, in general take place between initial levels and final levels of high probability. So electronic transi-
tions in a diatomic molecule are most likely to occur when the internuclear distance R is that of the center of
the range of motion when v = 0 and that of either extreme when v = 1, 2, 3,....

Now the selection rules for vibrational transitions do not hold for electronic transition between two electronic
states in a diatomic molecule.
Figure 2 shows three possible situations for electronic transitions.
➔ In a the average internuclear distances are the same in
both electronic states,
➔ In b the average distance is slightly greater in the upper
state, and
➔ In c it is much greater in the upper state.
When the molecule is in its ground state, the most probable value
of internuclear distance R is shown by the solid dot in the lowest
vibrational level 𝑣=0, where |ψ|2 is maximum.
According to the Franck-Condon principle, internuclear distance R
does not change when electronic transitions occur .
➢ In a , transition from 𝑣 = 0 lower level to 𝑣 = 0 of
the upper state is favored, because such a
transition connects configurations of high
probability.
Transitions to other vibrational levels 𝑣 = 1, 2, 3, of the
upper state also occur but produce weak absorption
lines, since |ψ|2 is maximum but small (but not 0) at the
central regions of the 𝑣 = 1, 2, 3, ... levels.
➢ In b, the favored transition is now at the end of the range of motion to the v = 1 upper level
state, since |ψ|2 is a maximum at the ends of the range of motion in the higher vibrational
levels. Transitions to the v = 0, 2, 3, and 4 levels take place as well, but again lead to weak lines.
➢ In c, an electronic transition is most likely to produce dissociation of the molecule; a transition
from the center of the lowest level intersects the upper potential-energy curve at a point
where no bound states are possible. However, transitions to bound states may also occur, but
with small probability, so the spectrum consists of several weak lines plus a continuum with no
line structure.

In fig d, a condition called pre- dissociation occurs because a transition from the center of the lowest level
intersects the upper potential-energy curve. Also, lower state has a minimum and the usual set of vibrational
levels, while the upper state has no minimum and accordingly is unstable. Thus, a transition from the ground
state to level d leads to the possibility that the molecule may be dissociated. Transition to higher states causes
dissociation of the molecule.