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Lecture 3

This document discusses the canonical partition function, which describes the probability of a system being in a particular microscopic state based on its energy. It can be used to calculate thermodynamic properties of the system. The partition function is the sum of exponential terms accounting for the probability and degeneracy of each energy state. For independent energy modes, like translation and rotation, the total partition function is the product of the individual mode partition functions. For a collection of non-interacting identical atoms, the partition function is the product of single-atom partition functions divided by N! to account for atomic indistinguishability.

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35 views16 pages

Lecture 3

This document discusses the canonical partition function, which describes the probability of a system being in a particular microscopic state based on its energy. It can be used to calculate thermodynamic properties of the system. The partition function is the sum of exponential terms accounting for the probability and degeneracy of each energy state. For independent energy modes, like translation and rotation, the total partition function is the product of the individual mode partition functions. For a collection of non-interacting identical atoms, the partition function is the product of single-atom partition functions divided by N! to account for atomic indistinguishability.

Uploaded by

Sima Kumari
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Applied Statistical Thermodynamics

Module 2:Canonical Partition Function


Lecture 1: Properties of the Canonical Partition Function
Content

 Properties of Canonical Partition Function

 Thermodynamic Quantities from the Partition Function

 Canonical Partition Function for Independent Energy Modes


Canonical Partition Function
 Probability of occurrence of a particular microstate i with energy Eα

 What is the probability of finding the system in any microstate such that its energy is Eα?
Canonical Partition Function
 Probability of occurrence of a particular microstate i with energy Eα

 Probability of occurrence of energy level Eα


Canonical Partition Function

 Probability of occurrence of a particular microstate i decreases with energy

 Particular state with a lower energy is more probable than a particular state with a higher
energy

 Degeneracy is an increasing function of energy level

 Probability that the macroscopic system will have an energy level Eα

 product of an exponential term that is decreasing with increasing energy and


 Degeneracy that is increasing with increasing energy
Canonical Partition Function
Canonical Partition Function: Thermodynamic Properties

 Internal Energy: the average value of the energy of the system


Canonical Partition Function for Independent Energy Modes

 Translational Mode: Mass and Center of Mass Velocity

 Rotational Mode: Moment of Inertia and Rotational Velocity


Canonical Partition Function for Independent Energy Modes

 Translational Mode: Mass and Center of Mass Velocity

 Rotational Mode: Moment of Inertia and Rotational Velocity


Canonical Partition Function for Independent Energy Modes

 Canonical Partition function is then the product of the partition function of the Individual
Energy modes
Canonical Partition Function for Collection of Non-Interacting
Identical Atoms
 Canonical Partition function is then the product of the partition function of the Individual
Energy modes

 N such identical atoms sufficiently far apart


 Neglect their potential energy of interaction
 have only translational energy

 Can we specify the energy state of each atom ?

 prohibited by the Heisenberg uncertainty principle : position and velocity of each


atom at an instant are imperfectly
 Rather than specifying the energy state of each atom,

 Define a state of the system by specifying the number of atoms in each energy
state, but not indicating which atoms are in that state
Canonical Partition Function for Collection of Non-Interacting
Identical Atoms
 nij is the occupation number, or the number of atoms in the jth atomic state of a single
atom in the ith macroscopic state of the collection of atoms
Canonical Partition Function for Collection of Non-Interacting
Identical Atoms
 nij is the occupation number, or the number of atoms in the jth atomic state of a single
atom in the ith macroscopic state of the collection of atoms
Canonical Partition Function for Collection of Non-Interacting
Identical Atoms
Collection of Non-Interacting Identical Atoms: Inferences

 Energy modes are independent, but distinguishable

 Difference between a translational motion and a rotation


 Total partition function is the product of the partition functions for each of the
energy modes.

 Individual atoms are independent but indistinguishable from each other

 Total partition function is the product of the individual atom partition functions
 Divided by the factor N! as a result of the indistinguishability of the atoms
Course Material
References

 S. I. Sandler, An Introduction to Applied Statistical Thermodynamics. John Wiley & Sons. Hoboken, NJ, 2010
 D. A. McQuarrie, Statistical Mechanics, University Science Books, Sausalito, CA, 2000
 D. Chandler, Introduction to Modern Statistical Mechanics, Oxford University Press, London, 1987.
 M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids, Clarendon Press, Oxford, 1989

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