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Statistical Molecular Thermodynamics: Christopher J. Cramer

This document summarizes key concepts from Week 3 of a course on statistical molecular thermodynamics. It discusses how the probability of a state being populated decreases exponentially with energy and is determined by temperature. It also reviews the canonical ensemble with fixed N, V, and T, and how the partition function Q relates to accessible states. Various macroscopic properties can be computed as ensemble averages weighted by state probabilities. The partition function for non-interacting particles can be written as a product of single-particle partition functions. Molecular partition functions can also be expressed as products of translational, rotational, vibrational, and electronic terms.

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40 views4 pages

Statistical Molecular Thermodynamics: Christopher J. Cramer

This document summarizes key concepts from Week 3 of a course on statistical molecular thermodynamics. It discusses how the probability of a state being populated decreases exponentially with energy and is determined by temperature. It also reviews the canonical ensemble with fixed N, V, and T, and how the partition function Q relates to accessible states. Various macroscopic properties can be computed as ensemble averages weighted by state probabilities. The partition function for non-interacting particles can be written as a product of single-particle partition functions. Molecular partition functions can also be expressed as products of translational, rotational, vibrational, and electronic terms.

Uploaded by

Alvaro
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Statistical Molecular

Thermodynamics
Christopher J. Cramer
Video 3.8
Review of Week 3

Critical Concepts from Week 3

The probability of a state in an ensemble being populated


decreases exponen7ally with its energy; temperature dictates
the rapidity of that exponen7al decay

The canonical ensemble involves xed number (N), volume (V),


and temperature (T)

The par77on func7on Q is a measure of the number of


accessible states at a given temperature

The ra7o of, the exponen7al of the energy of a given state


divided by kBT, rela7ve to Q, provides the probability of a
member of the ensemble being in that state

Various macroscopic proper7es can be computed as averages of


proper7es weighted by ensemble probabili7es

Critical Concepts from Week 3

For non-interac7ng par7cles, the par77on func7on of an


ensemble can be wriEen as the product of par77on func7ons for
the individual par7cles.

The macroscopic internal energy of a monatomic ideal gas is


related to the ensemble average energy for an appropriate
par77on func7on (so, too, is the molar heat capacity)

The macroscopic pressure of a monatomic ideal gas is related to


the ensemble average pressure for an appropriate par77on
func7on and predicts the ideal gas equa7on of state

Another par77on func7on for a gas can be shown to be consistent


with the van der Waals equa7on of state

Critical Concepts from Week 3

Par77on func7ons for dis(nguishable vs indis(nguishable non-


interac7ng par7cles dier by a factor of (N!)1

Molecular par77on func7ons can themselves be expressed as


products of transla7onal, rota7onal, vibra7onal, and electronic
par77on func7ons

Par77on func7ons expressed over states can be related to


par77on func7ons expressed over energy levels through inclusion
of the degeneracy in the par77on func7on sum

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