Applied Statistical Thermodynamics

Module 1:Introduction to Statistical Thermodynamics

Lecture 2: Postulates and Boltzmann Distribution
Content

 Postulates of Statistical Mechanics

 Boltzmann Energy Distribution

 Canonical Partition Function

Postulates
 All microstates of the system of volume V that have the same energy and the same
number of particles are equally probable

 equal a priori probability principle

 Tells us how to choose a probability distribution

Postulates
 The (long) time average of any mechanical property in a real macroscopic system is
equal to the average value of that property over all the microscopic states of the system,
each state weighted with its probability of occurrence, provided that the microscopic
states replicate the thermodynamic state and environment of the actual system.

 Also called as Ergodic Hypothesis

 experimental measurement is really a long time measurement on a molecular time scale

 The first postulate tells us how to choose the probability distribution

 Second postulate establishes that thermodynamic properties computed with this

probability distribution will be equivalent to those that we would measure

 Replacement of Time Average with Statistical Average

Boltzmann Distribution Function
 Assign probabilities to states of different energies for a system of fixed volume and
number of particles in contact with a large heat bath

 macroscopic subsystems A and B are in contact with an infinite heat bath of constant
temperature

 As the heat source is so large that, A and B are unaffected by the presence of one
another

 Fluctuation of energy or temperature in system A has no effect on system B, and vice

versa
Boltzmann Distribution Function
 Defining the Probabilities of System A and B

 What is the probability of simultaneously finding system A in sA and B in sB ?

Boltzmann Distribution Function

 What is the Probability of finding the composite system(A+B) in a particular microstate

sAB ?

 How does the probabilities change with respect to Em or En?

 Energies are closely spaced and can be assumed as a continuous variable

 Compute the probability change with respect to energy

Boltzmann Distribution Function
Boltzmann Distribution Function

 Left-hand side is independent of subsystem B, and the right-hand side of the equation is independent of subsys-
tem A

 Each side of that equation must be independent of both subsystems A and B and can only depend on the
properties of the reservoir
Boltzmann Distribution Function
Canonical Partition Function
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