Let consider the translational partition function of a monatomic gas.

Consider a molecule
confined to a cubic box. A molecule inside a cubic box of length LL has the translational energy
levels given by

Etr=h2(n2x+n2y+n2z)8mL2(18.1.1)(18.1.1)Etr=h2(nx2+ny2+nz2)8mL2

where nxnx, nyny and nznz are the quantum numbers in the three directions. The translational
partition function is given by

qtr=∑ie−ϵi/kBT(18.1.2)(18.1.2)qtr=∑ie−ϵi/kBT

which is the product of translational partition functions in the three dimensions.

qtr=∑nx=1∞e−ϵx/kBT∑ny=1∞e−ϵy/kBT∑nz=1∞e−ϵz/kBT(18.1.3)(18.1.3)qtr=∑nx=1∞e−ϵx/kBT∑ny=1∞e−ϵy/kBT∑nz=
1∞e−ϵz/kBT

qtr=qxqyqz(18.1.4)(18.1.4)qtr=qxqyqz

Since the levels are very closely spaced, we can replace each sum in Equation 18.1.318.1.3 with
an integral, for example:

qx=∑nx=1∞e−ϵx/kBT≈∫∞nx=1e−ϵx/kBT(18.1.5)(18.1.5)qx=∑nx=1∞e−ϵx/kBT≈∫nx=1∞e−ϵx/kBT

and after substituting the energy for the relevant dimension

ϵx=h2n2x8mL2(18.1.6)(18.1.6)ϵx=h2nx28mL2

we can extend the lower limit of integration in the approximation of Equation 18.1.518.1.5

qx=∫∞1e−h2n2x8mL2kBT≈∫∞0e−h2n2x8mL2kBT(18.1.7)(18.1.7)qx=∫1∞e−h2nx28mL2kBT≈∫0∞e−h2nx28mL2kBT

we then use the following solved Gaussian integral

∫∞oe−an2dn=π4a−−−√(18.1.8)(18.1.8)∫o∞e−an2dn=π4a

with the following substituion

a=h28mL2kBT(18.1.9)(18.1.9)a=h28mL2kBT

we get,

qx=12πa−−√=12π8mkBTh2−−−−−−−−√L(18.1.10)(18.1.10)qx=12πa=12π8mkBTh2L

or more commonly presented as

qx=LΛ(18.1.11)(18.1.11)qx=LΛ

where ΛΛ is the de Broglie thermal wavelength and is given by

Λ=h2π8mkbT−−−−−−−−√(18.1.12)(18.1.12)Λ=h2π8mkbT

Multiplying the expressions for qxqx, qyqy and qzqz (Equation 18.1.418.1.4) and using VV as the
volume of the box L3L3, we arrive at
 qtr=(2π8mkbT−−−−−−−−√h)3/2V=VΛ3(18.1.13)(18.1.13)qtr=(2π8mkbTh)3/2V=VΛ3

This is usually a very large number (1020) for volumes of 1 cm3 for a typical small molecular
masses. This means that such a large number of translational states are accessible available for
occupation by the molecules of a gas. This result is very similar to the result of the classical
kinetic gas theory that said that the observed energy of an ideal gas should read as

U=32nRT(18.1.14)(18.1.14)U=32nRT

We postulate therefore that the observed energy of a macroscopic system should equal the
statistical average over the partition function as shown above. In other words: if you know the
particles your system is composed of and their energy states you can use statistics to calculate
what you should observe on the whole ensemble.

EXAMPLE

Calculate the translational partition function of an I2I2 molecule at 300K. Assume V to be 1 liter.

Solution

Mass of I2I2 is 2×127×1.6606×10−27kg2×127×1.6606×10−27kg

2πmkBT=2×3.1415×(2×127×1.6606×10−27kg)×1.3807×10−23J/K×300K(18.1.15)(18.1.15)2πmkBT=
2×3.1415×(2×127×1.6606×10−27kg)×1.3807×10−23J/K×300K

=1.0969×10−44Jkg(18.1.16)(18.1.16)=1.0969×10−44Jkg

Λ=h2πmkBT−−−−−−−√(18.1.17)(18.1.17)Λ=h2πmkBT

=6.6262×10−34Js1.0969×10−44Jkg−−−−−−−−−−−−−−−√=6.326×10−12m(18.1.18)(18.1.18)=6.6262×1
0−34Js1.0969×10−44Jkg=6.326×10−12m

qtr=VΛ3=1000×10−6m3(6.326×10−12m)3=3.95×1030(18.1.19)(18.1.19)qtr=VΛ3=1000×10−6m3(6.326
×10−12m)3=3.95×1030

This means that 3.95×10303.95×1030 quantum states are thermally accessible to the molecular
system

18.6: Rotational Partition Functions of Diatomic Gases

1. Last updated
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2.
o 18.5: Most Molecules are Rotationally Excited at Ordinary Temperatures

o 18.7: Vibrational Partition Functions of Polyatomic Molecules

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The rotational energy levels of a diatomic molecule are given by

Erot(J)=B~J(J+1)(18.6.1)(18.6.1)Erot(J)=B~J(J+1)
where

B~=h8π2Ic(18.6.2)(18.6.2)B~=h8π2Ic

Here, B~B~ is the rotational constant expressed in cm-1. The rotational energy levels are given by

Ej=J(J+1)h28πI(18.6.3)(18.6.3)Ej=J(J+1)h28πI

where II is the moment of inertia of the molecule given by μr2μr2 for a diatomic and μμ is the reduced
mass and rr the bond length (assuming rigid rotor approximation). The energies can be also expressed in
terms of the rotational temperature, ΘrotΘrot, which is defined as

Θrot=r28π2Ik(18.6.4)(18.6.4)Θrot=r28π2Ik

In the summation for the expression for rotational partition function (qrotqrot), Equation 18.6.518.6.5, we
can do an explicit summation

qrot=∑j=0(2J+1)e−EJ/kBT(18.6.5)(18.6.5)qrot=∑j=0(2J+1)e−EJ/kBT

if only a finite number of terms contribute. The factor (2J+1)(2J+1) for each term in the expansion
accounts for the degeneracy of a rotational state JJ. For each allowed energy EJEJ from
Equation 18.6.118.6.1, then there are (2J+1)(2J+1) states eigenstates it, then, the Boltzmann
factor e−EJ/kBTe−EJ/kBT has to be multiplied by (2J+1)(2J+1) to properly account for all these states.

If the rotational energy levels are lying very close to one another, we can integrate similar to what we did
for qtransqtrans previously to get

qrot=∫∞0(2J+1)R−B~J(J+1)/kBTdJ(18.6.6)(18.6.6)qrot=∫0∞(2J+1)R−B~J(J+1)/kBTdJ

This the integration can be easily be done by substituting x=J(J+1)x=J(J+1) and dx=(2J+1)dJdx=(2J+1)dJ

qrot=kBTB~(18.6.7)(18.6.7)qrot=kBTB~

For a homonuclear diatomic molecule, rotating the molecule by 180° brings the molecule into a
configuration which is indistinguishable from the original configuration. This leads to an overcounting of
the accessible states. To correct for this, we divide the partition function by σσ, which is called
the symmetry number, which is equal to the distinct number of ways by which a molecule can be brought
into identical configurations by rotations. The rotational partition function becomes,

qrot=kTB~σ(18.6.8)(18.6.8)qrot=kTB~σ

or commonly expressed in terms of ΘrotΘrot

qrot=TΘrotσ(18.6.9)(18.6.9)qrot=TΘrotσ

EXAMPLE 18.6.118.6.1

What is the rotational partition function of H2H2 at 300 K?

Solution
The value of B~B~ for H2H2 is 60.864 cm-1. The value of kBTkBT in cm-1 can be obtained by dividing it
by hchc, i.e., which is kBT/hc=209.7cm−1kBT/hc=209.7cm−1 at 300 K. σ=2σ=2 for a homonuclear
molecule. Therefore from Equation 18.6.818.6.8,

qrot=kBTB~σ=209.7cm−1(2)(60.864cm−1)=1.723qrot=kBTB~σ=209.7cm−1(2)(60.864cm−1)=1.723

Since the rotational frequency of H2H2 is quite large, only the first few rotational states are accessible at
300 K