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Chemistry LibreTexts

Rotational Partition Functions (Worksheet)

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The partition function for a single atom or molecule can be expressed

q(V)=ieϵi/kBT

where ϵi describes the energy of the atom or molecule (e.g., derived from solving the Schrödinger equation for a specific system). For systems that exhibit a degeneracy of eigenstates (for example in rotation or electronic spectroscopy), Equation ??? is modified

q(V)=igieϵi/kBT

where gi is the degeneracy of the ith eigenstate.

Q1

We can model rotational motion as a rigid rotor quantum problem with the following expression for energies

ϵJ=h2J(J+1)2I

where I is the moment of inertia. For a diatomic molecule

I=mR2eq

The degeneracy is gJ=2J+1 for a rigid rotor.

Substitute your the energies and degenerates into Equation ??? for the starting equation of the rotational molecular partition function.

Q2

While the spacing of the energy levels for a rigid rotor are appreciable bigger than for translation, they are are often quite small relative to thermal energy KBT at ambient temperature. This means that we can approximate the sum derived in Q1 with an integral, just like in the translation partition function. Write this integral and pay attention to the limits of integration.

Q3

Since the differential below can be expanded

d[J(J+1)]=d[J2+J]=(2J+1)dJ

the integral derived in Q2 can be expressed in terms of d[J(J+1)] instead of dJ. Write this integral.

Q4

The integral in Q3 is an exponential integral with a known solution (e.g., via an integration table). Use that solution to obtain the final form of the rotational partition constant (of a diatomic molecule)

qrot=8πIkBh2T=ΘrT

where Θr is the rotational temperature for the molecule (akin to the thermal de Brogle wavelength in the translation partition function).

Q5

What is the rotational partition function of B2 at 300 K? How does this compare to the diatomic molecule's corresponding translational partition function? How do you interpret this comparison (in words)?


This page titled Rotational Partition Functions (Worksheet) is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by Nancy Levinger.

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