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Statistical Mechanics: Course Code - PPHY 302

This document discusses statistical mechanics and the canonical ensemble. It introduces key concepts like microstates, macrostates, and the canonical distribution. The partition function Z is defined, which contains all information about a system's energy states. Thermodynamic quantities like internal energy, entropy, heat capacity, and pressure can be derived from the partition function using standard procedures. Examples are given of calculating the partition function for different systems like a two-level system and harmonic oscillator.

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Siva Arun
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61 views

Statistical Mechanics: Course Code - PPHY 302

This document discusses statistical mechanics and the canonical ensemble. It introduces key concepts like microstates, macrostates, and the canonical distribution. The partition function Z is defined, which contains all information about a system's energy states. Thermodynamic quantities like internal energy, entropy, heat capacity, and pressure can be derived from the partition function using standard procedures. Examples are given of calculating the partition function for different systems like a two-level system and harmonic oscillator.

Uploaded by

Siva Arun
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Aum Sri Sai Ram

Statistical Mechanics
Course Code - PPHY 302
Lecture - 4
Recap
Concept of Microstates and Macrostates

Concept of ensembles & different types of ensembles

Canonical ensemble

Canonical distribution; Boltzmann factor; Partition function


2
Applications of Boltzmann distribution

Notation

1. The two-state system

In a two-state system, there are only two states, one with energy 0 and
the other with energy

Aim: To compute the average energy of the system?

3
i = 1, 2

The probability of being in the lower state is given by

The probability of being in the upper state is

4
The average energy E of the system is then

5
2. Chemical reactions

Many chemical reactions have an activation energy E_act of about 1/2 eV.

At T = 300 K, which is about room temperature, the probability that

a particular reaction occurs is proportional to

If the temperature is increased to T + ΔT = 310 K, the probability

increases to

6
This probability is larger by a factor

Hence many chemical reactions roughly double in speed when the

temperature is increased by about 10 K.


7
Definition of entropy
From thermodynamics

From first law of thermodynamics we have

Mathematically we can write dU as

8
Equivalently we can write

Recall

9
This is the expression for the entropy of a system that is in a

particular macrostate in terms of Ω, the number of microstates associated

with that macrostate.

Connection between macroscopic thermodynamic property and


microstates.

10
Gibbs formula for entropy

11
Can we derive other macroscopic thermal properties
from the microscopic description?

12
The partition function
The probability that a system is in some particular microstate α is propor-

tional to the Boltzmann factor

The partition function Z is defined as a sum over all the states of the

Boltzmann factors, so that

where the sum is over all states of the system (each one labelled by α).

13
The partition function Z contains all the information about the energies

of the states of the system.

The fantastic thing about the partition function is that all thermodynamic
quantities can be obtained from it.

14
Therefore problem solving in Statistical Mechanics can be reduced to two
steps:

1. Write down the partition function Z


2. Go through some standard procedures to obtain the functions of state
we want from Z

15
1. Writing down the partition function

Nothing more than evaluating this expression for a


given situation

Few examples...

16
The two-level system

Let the energy of a system be either −Δ/2 or Δ/2. Then

17
The simple harmonic oscillator
The energy of the system is ħ

where n = 0, 1, 2, . . .,

ħ
ħ ħ ħ
ħ

(Sum of an infinite geometric series)


18
The N - level system
Let the energy levels of a system be

0, ħω, 2 ħω, ... , (N-1)ħω

ħ
ħ
ħ

The sum is evaluated using the standard result for the sum of a finite geometric
progression.
19
Rotational energy levels
The rotational kinetic energy of a molecule with moment of inertia I is

given by where is the total angular momentum operator.

The energy levels of this system are given by ħ

and have degeneracy (2J + 1).

The partition function is

where the factor (2J +1) takes into account the degeneracy of each level. 20
Obtaining the functions of state

21
Internal energy
The internal energy U is given by

Now the denominator of this expression is the partition function, Z.

The numerator is simply

22
Entropy

Gibbs entropy
formula

We have used
23
Helmholtz function
Helmholtz function, F = U-TS

24
Heat capacity

Or

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Pressure

Having got the pressure, we can write down the enthalpy and the Gibbs
function.

26
Enthalpy

27
Gibbs function

28
Thermodynamic quantities derived from the partition
function Z

29

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