References:: A) Physical Chemistry by Atkins B) Physical Chemistry: A Molecular Approach by Simon and Quarrie

Further Insights on Statistical mechanics:
Rotational Motion of Molecules

References:
a) Physical Chemistry by Atkins
b) Physical Chemistry: A Molecular Approach by Simon and Quarrie
https://www.youtube.com/watch?v=ZoCLSb0HQJ8 https://www.youtube.com/watch?v=hx0tSiCQWDc
Rotational Motion in Rigid- Rotator
To develop the theory for a diatomic molecule, so that its rotational
partition function is understood, we need the following relatively simple
background (McQuarrie, 1997).
As the distance between the two masses is fixed, this model is referred
to as the rigid-rotator model. Even though a diatomic molecule vibrates
as it rotates, the vibrational amplitude is small compared with the bond
length, so considering the bond length fixed is a good approximation
To develop the theory for a diatomic molecule, so that its rotational
partition function is understood, we need the following relatively simple
background (McQuarrie, 1997).
As the distance between the two masses is fixed, this model is referred
to as the rigid-rotator model. Even though a diatomic molecule vibrates
as it rotates, the vibrational amplitude is small compared with the bond
length, so considering the bond length fixed is a good approximation
We do a bit of nifty math here. We combine this system into a whole by
using a combined mass of the two-body problem and an effective
distance of this reduced mass from the axis of rotation
Reduced mass
𝑚1 𝑚2
𝜇=
𝑚1 + 𝑚2
𝑚1 𝑚2 2
𝐼= 𝑟 = 𝑚1 𝑟12 + 𝑚2 𝑟22
𝑚1 + 𝑚2
We do a bit of nifty math here. We combine this system into a whole by
using a combined mass of the two-body problem and an effective
distance of this reduced mass from the axis of rotation
𝑚1 𝑚2
Reduced mass 𝜇=
𝑚1 +𝑚2
𝑚1 𝑚2 2
𝐼= 𝑟 = 𝑚1 𝑟12 + 𝑚2 𝑟22
𝑚1 + 𝑚2
What is r? We also know that about the centre of mass
𝑚1 𝑟1 = 𝑚2 𝑟2
𝑚1 𝑚2 𝑚1 𝑚2 2
Reduced mass 𝜇= 𝐼= 𝑟 = 𝑚1 𝑟12 + 𝑚2 𝑟22
𝑚1 +𝑚2 𝑚1 + 𝑚2
What is r? We also know that about the centre of mass
𝑚1 𝑟1 = 𝑚2 𝑟2
Cross-multiply the above equation for I to get
𝑚1 𝑚2 𝑟 2 = 𝑚12 𝑟12 + 𝑚1 𝑚2 𝑟12 + 𝑚22 𝑟22 + 𝑚1 𝑚2 𝑟22
Using the nice fact that 𝑚1 𝑟1 = 𝑚2 𝑟2 we find that
𝑚1 𝑚2 𝑟 2 = 𝑚1 𝑚2 𝑟1 𝑟2 + 𝑟12 + 𝑟1 𝑟2 + 𝑟22
Hence, we find elegantly that
𝑟 2 = 𝑟1 + 𝑟2 2
𝑚1 𝑚2 2
𝐼= 𝑟 = 𝑚1 𝑟12 + 𝑚2 𝑟22
𝑚1 + 𝑚2
𝑟 2 = 𝑟1 + 𝑟2 2
From the above equation, the overall system may be reduced to the
moment of inertia of a single body of mass rotating at a distance r from a
fixed center. Thus, we have transformed a two-body problem into an
equivalent one-body problem.
Operators and their Significance
𝐿෠2 =
We do not have potential energy in this problem as there are no

external magnetic or electric fields. The energy of the molecule does
not depend on its orientation in space.
෡ is therefore just the
The Hamiltonian operator of a rigid rotator 𝐻
෡ given in the next
kinetic energy operator, and using the operator 𝐾
table we can write as follows for a rigid rotator as
where ∇2 is the Laplacian operator. Therefore, we must convert ∇2 from

Cartesian coordinates to spherical coordinates.
where ∇2 is the Laplacian operator.

If the system has a natural center of symmetry, such as one particle
revolving around one fixed at the origin, then using spherical
coordinates is much more convenient. Note that the rigid rotator
involves constant r.
Therefore, we must convert ∇2 from Cartesian coordinates to
spherical coordinates. The final result is
Now plugging the spherical coordinates-based Laplacian in the first equation

shown above, we get
𝐿෠2
෡=
Since the kinetic energy is equal to 𝐻 we get
2𝐼
𝐿෠2 =
The orientation of a linear rigid rotator is completely specified by the

two angles  and , so rigid-rotator wave functions depend upon only
these two variables.
The rigid-rotator wave functions are customarily denoted by Y(,),
so the Schrodinger equation for a rigid rotator reads
If we multiply the above equation by sin2 and let
We get the following relation

The solutions to the above equation are the rigid-rotator wave functions.
When we solve the above equation, it turns out naturally that , must
obey the condition
From the definition of and the above equation we get

We obtain a set of discrete energy levels.

In addition to the allowed energies given by equation above,
we also find that each energy level has a degeneracy gj given by
gj = 2 J + 1
Rotational Motion in Rigid- Rotator Representing
Rotation of a Diatomic Molecule
We obtain a set of discrete energy levels.

𝑔𝑗 = 2 𝐽 + 1.
The selection rule for the rigid rotator says that transitions are allowed only
between adjacent states or that
𝐽 = ±1
Rotational Motion in Rigid- Rotator Representing
Rotation of a Diatomic Molecule
In the case of absorption of electromagnetic radiation, the molecule goes

from a state with a quantum number J to one with J + 1. The energy
difference, then, is
In addition to the requirement that  J = ±1, the molecule must also have a
permanent dipole moment to absorb electromagnetic radiation. Thus, HCI has
a rotational spectrum, but N2 does not.

Representing Rotation of a Diatomic Molecule
Using the Bohr frequency condition 𝐸 = 𝐸𝑖+1 − 𝐸𝑖 = ℎ𝑣 ,

the frequencies at which the absorption transitions occur are
The reduced mass of a diatomic molecule is typically around
10-25 to 10-26 kg,
and a typical bond distance is approximately 10-10 m (100
pm),
Therefore, the moment of inertia of a diatomic molecule
typically ranges from 10-45 to 10-46 kg·m2.

Substituting I=5 X 10-46 kg.m2 into
gives that the absorption frequencies are about 2 x 1010 to
1011 Hz.
We see that these frequencies lie in the microwave region.
Consequently, rotational transitions of diatomic molecules
occur in the microwave region, and the direct study of
rotational transitions in molecules is called microwave
spectroscopy.
It is common practice in microwave spectroscopy to write
following equation
as
B is called as the rotational constant of the molecule.
Also, the transition frequency is commonly expressed in terms of wave
numbers ෤ (cm-1) rather than hertz (Hz). If we use the relation

෤ =
𝑐
then
෨ is given in terms of wavenumbers

where the rotational constant 𝐵
From either of the two equations in terms of frequency or wavenumber,

we see that the rigid-rotator model predicts that the microwave
spectrum of a diatomic molecule consists of a series of equally spaced
lines with a separation of 2B Hz or 2𝐵෨ cm-1 as shown in Figure.
From the separation between the absorption frequencies, we can

determine the rotational constant and hence the moment of inertia of the
molecule. Furthermore, we find r from
I =r2 (r = internuclear distance or bond length)
From the separation between the absorption frequencies, we can

determine the rotational constant and hence the moment of inertia of the
molecule. Furthermore, we find r from
I =r2 (r = internuclear distance or bond length)
A diatomic molecule is not truly a rigid rotator, because it simultaneously

vibrates, however small the amplitude. Consequently, we might expect that
although the microwave spectrum of a diatomic molecule consists of a
series of lines, their separation is not exactly constant. Corrections are
available for the fact that the bond is not exactly rigid.
Rotational Partition Function
Inserting the expression for the energy into that for the
partition function, and taking the degeneracy of rotational
levels into account, yields
∞ 𝑗 𝑗+1 ℎ2
1 − 2
𝑞𝑟𝑜𝑡 = ෍(2𝑗 + 1)𝑒 8𝜋 𝐼𝑘𝐵 𝑇
𝜎
𝑗=0
𝑗 𝑗+1 ℎ 2
1 ∞ − 2
≈ න 𝑑 𝑗 𝑗 + 1 𝑒 8𝜋 𝐼𝑘𝐵 𝑇
𝜎 0
1 8𝜋 2 𝐼𝑘𝐵 𝑇 ℎ2
= for 𝑇 > 2
𝜎 ℎ2 8𝜋 𝐼𝑘𝐵
Rotational (and Nuclear) Partition Function
The final expression is the classical limit, valid above a certain critical temperature,
which, however, in practical cases is low (i.e. 85 K for H2, 3 K for CO).
For a homonuclear or a symmetric linear molecule, the factor 𝜎 equals 2, while for a
heteronuclear molecule 𝜎 = 1 (Table below).

References:: A) Physical Chemistry by Atkins B) Physical Chemistry: A Molecular Approach by Simon and Quarrie

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References:: A) Physical Chemistry by Atkins B) Physical Chemistry: A Molecular Approach by Simon and Quarrie

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Further Insights on Statistical mechanics:

Rotational Motion of Molecules

What is r? We also know that about the centre of mass

𝑚1 𝑚2 𝑟 2 = 𝑚12 𝑟12 + 𝑚1 𝑚2 𝑟12 + 𝑚22 𝑟22 + 𝑚1 𝑚2 𝑟22

Using the nice fact that 𝑚1 𝑟1 = 𝑚2 𝑟2 we find that

We do not have potential energy in this problem as there are no

where ∇2 is the Laplacian operator. Therefore, we must convert ∇2 from

where ∇2 is the Laplacian operator.

Now plugging the spherical coordinates-based Laplacian in the first equation

The orientation of a linear rigid rotator is completely specified by the

If we multiply the above equation by sin2 and let

We get the following relation

From the definition of and the above equation we get

We obtain a set of discrete energy levels.

We obtain a set of discrete energy levels.

In the case of absorption of electromagnetic radiation, the molecule goes

permanent dipole moment to absorb electromagnetic radiation. Thus, HCI has

a rotational spectrum, but N2 does not.

Using the Bohr frequency condition 𝐸 = 𝐸𝑖+1 − 𝐸𝑖 = ℎ𝑣 ,

The reduced mass of a diatomic molecule is typically around

10-25 to 10-26 kg,

and a typical bond distance is approximately 10-10 m (100

Therefore, the moment of inertia of a diatomic molecule

typically ranges from 10-45 to 10-46 kg·m2.

Substituting I=5 X 10-46 kg.m2 into

gives that the absorption frequencies are about 2 x 1010 to

We see that these frequencies lie in the microwave region.

Consequently, rotational transitions of diatomic molecules

occur in the microwave region, and the direct study of

rotational transitions in molecules is called microwave

෨ is given in terms of wavenumbers

From either of the two equations in terms of frequency or wavenumber,

From the separation between the absorption frequencies, we can

From the separation between the absorption frequencies, we can

A diatomic molecule is not truly a rigid rotator, because it simultaneously

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