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STATISTICAL PHYSICS
BASICS OF

A Bachelor Degree Introduction

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Basics of Statistical Physics Downloaded from www.worldscientific.com

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BASICS OF

STATISTICAL PHYSICS
A Bachelor Degree Introduction

Harald J W Mller-Kirsten
University of Kaiserslautern, Germany

World Scientific
NEW JERSEY

LONDON

SINGAPORE

BEIJING

SHANGHAI

HONG KONG

TA I P E I

CHENNAI

Published by
World Scientific Publishing Co. Pte. Ltd.
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British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

BASICS OF STATISTICAL PHYSICS

A Bachelor Degree Introduction
Copyright 2010 by World Scientific Publishing Co. Pte. Ltd.
All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means,
electronic or mechanical, including photocopying, recording or any information storage and retrieval
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ISBN-13 978-981-4287-22-7
ISBN-10 981-4287-22-9

Printed in Singapore.

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Contents
Preface

ix

1 Introduction
1.1 Introductory Remarks . . . . . . . .
1.2 Thermodynamic Potentials . . . . .
1.3 Capacity of Heat . . . . . . . . . . .
1.4 Frequently Used Terms . . . . . . . .
1.5 Applications and Examples . . . . .
1.6 Problems without Worked Solutions

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2 Statistical Mechanics of an Ideal Gas (Maxwell)

2.1 Introductory Remarks . . . . . . . . . . . . . . . .
2.2 Maxwells Treatment . . . . . . . . . . . . . . . . .
2.3 Lagranges Method of Multipliers . . . . . . . . . .
2.4 Applications . . . . . . . . . . . . . . . . . . . . . .
2.4.1 Pressure exerted on the wall of a vessel . .
2.4.2 Effusion of gas through a hole . . . . . . . .
2.4.3 Thermionic emission . . . . . . . . . . . . .
2.5 Distribution Function for all Directions . . . . . .
2.6 Applications and Examples . . . . . . . . . . . . .
2.7 Problems without Worked Solutions . . . . . . . .
3 The
3.1
3.2
3.3
3.4
3.5
3.6

a priori Probability
Introductory Remarks . . . . . . . . . . .
The a priori Probability . . . . . . . . . .
Examples Illustrating Liouvilles Theorem
Insertion of Physical Conditions . . . . . .
Applications and Examples . . . . . . . .
Problems without Worked Solutions . . .
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vi
4 Classical Statistics (MaxwellBoltzmann)
4.1 Introductory Remarks . . . . . . . . . . . . . . . .
4.2 The Number of Arrangements of Elements in
MaxwellBoltzmann Statistics . . . . . . . . . . . .
4.3 Method of Maximum Probability . . . . . . . . . .
4.3.1 The case of nonconserved elements . . . . .
4.3.2 The case of conserved elements . . . . . . .
4.3.3 The meaning of . . . . . . . . . . . . . .
4.3.4 Identification of with 1/kT . . . . . . . .
4.3.5 Distribution of particles in the atmosphere
4.3.6 Law of equipartition of energy . . . . . . .
4.4 Applications . . . . . . . . . . . . . . . . . . . . . .
4.4.1 The monatomic gas . . . . . . . . . . . . .
4.4.2 A solid . . . . . . . . . . . . . . . . . . . . .
4.5 Applications and Examples . . . . . . . . . . . . .
4.6 Problems without Worked Solutions . . . . . . . .

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5 Entropy
5.1 Introductory Remarks . . . . . . . .
5.2 The Boltzmann Formula . . . . . . .
5.3 Applications and Examples . . . . .
5.4 Problems without Worked Solutions

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6 Quantum Statistics
6.1 Introductory Remarks . . . . . . . . . . . . . . . . . .
6.2 A priori Weighting in Quantum Statistics . . . . . . .
6.2.1 Approximate calculation of number of states .
6.2.2 Accurate calculation of number of states . . . .
6.2.3 Examples . . . . . . . . . . . . . . . . . . . . .
6.3 The Allowed Number of Elements in Quantum States
6.3.1 One element . . . . . . . . . . . . . . . . . . .
6.3.2 Two non-interacting elements . . . . . . . . . .
6.3.3 More than two elements . . . . . . . . . . . . .
6.4 Counting of Number of Arrangements . . . . . . . . .
6.4.1 FermiDirac statistics . . . . . . . . . . . . . .
6.4.2 BoseEinstein statistics . . . . . . . . . . . . .
6.5 Quantum Statistics at High Temperatures . . . . . . .
6.6 Applications . . . . . . . . . . . . . . . . . . . . . . . .
6.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . .
6.8 Applications and Examples . . . . . . . . . . . . . . .
6.9 Problems without Worked Solutions . . . . . . . . . .

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7 Exact Form of Distribution Functions

7.1 Introductory Remarks . . . . . . . . .
7.2 FermiDirac Occupation Numbers . .
7.3 BoseEinstein Occupation Numbers .
7.4 Thermodynamical Functions . . . . . .
7.5 Applications and Examples . . . . . .
7.6 Problems without Worked Solutions .

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8 Application to Radiation (Light Quanta)

8.1 Introductory Remarks . . . . . . . . . . .
8.2 Plancks Radiation Law . . . . . . . . . .
8.3 Applications and Examples . . . . . . . .
8.4 Problems without Worked Solutions . . .
9 Debye Theory of Specific Heat of Solids
9.1 Introductory Remarks . . . . . . . . . .
9.2 The Calculation . . . . . . . . . . . . . .
9.3 Applications and Examples . . . . . . .
9.4 Problems without Worked Solutions . .
10 Electrons in Metals
10.1 Introductory Remarks . . . . . . . . . .
10.2 Evaluation of the Distribution Function
10.2.1 First approximation . . . . . . .
10.2.2 Second degree of approximation .
10.3 Applications and Examples . . . . . . .
10.4 Problems without Worked Solutions . .

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129
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11 Limitations of the Preceding Theory Improvement

with Ensemble Method
11.1 Introductory Remarks . . . . . . . . . . . . . . . . . . . .
11.2 Ensembles Three Types . . . . . . . . . . . . . . . . .
11.2.1 Ensembles and ergodic hypothesis . . . . . . . . .
11.2.2 The ensemble distribution function . . . . . . . . .
11.3 The Canonical Ensemble of a Closed System . . . . . . .
11.3.1 Thermodynamics of a closed system . . . . . . . .
11.4 The Grand Canonical Ensemble . . . . . . . . . . . . . . .
11.5 Ensemble Method of Maximum Probability . . . . . . . .
11.6 Comments on the Function . . . . . . . . . . . . . . . .
11.7 Applications and Examples . . . . . . . . . . . . . . . . .
11.8 Problems without Worked Solutions . . . . . . . . . . . .

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viii
12 Averaging instead of Maximization, and BoseEinstein
Condensation
12.1 Introductory Remarks . . . . . . . . . . . . . . . . . . . . . .
12.2 The DarwinFowler Method of Mean Values . . . . . . . . . .
12.2.1 Mean occupation number nj . . . . . . . . . . . . . . .
12.2.2 Taking subsidiary condition into account . . . . . . . .
12.3 Classical Statistics . . . . . . . . . . . . . . . . . . . . . . . .
12.4 Quantum Statistics . . . . . . . . . . . . . . . . . . . . . . . .
12.4.1 FermiDirac statistics . . . . . . . . . . . . . . . . . .
12.4.2 BoseEinstein statistics . . . . . . . . . . . . . . . . .
12.4.3 Evaluation of the coefficient of N in Z . . . . . . .
12.5 BoseEinstein Condensation . . . . . . . . . . . . . . . . . . .
12.5.1 The phenomenon of BoseEinstein condensation . . .
12.5.2 Derivation of the BoseEinstein distribution function
under condensation conditions . . . . . . . . . . . . .
12.6 Applications and Examples . . . . . . . . . . . . . . . . . . .
12.7 Problems without Worked Solutions . . . . . . . . . . . . . .

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191
201

Bibliography

203

Index

207

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Preface
Statistical physics more precisely statistical mechanics and statistical thermodynamics is almost universally the last of the four basic theory courses
for a degree in physics, and is usually taught after theory courses in mechanics, electrodynamics and quantum mechanics, thermodynamics proper, i.e.
classical thermodynamics, being usually combined with this or covered in
some form in connection with basic or experimental physics. Since the quantized form of statistical physics evolved naturally after the development of
quantum mechanics in the first half of the twentieth century, this was a natural sequence of steps. Prior to this development thermodynamics proper
was the additional basic subject of courses and examinations. The heavy
and detailed monograph of Mayer and Mayer [29], first published in 1940,
shows how quickly the entire basis of quantum statistics was developed with
numerous concurrent applications, so that soon appropriate texts appeared.
One of these later texts was the book of Schrodinger [39]. This was the
recommended text when the author had his first encounter with quantum
statistics in 1956 in the second half of the third and final year for the Bachelor of Science degree (the Honours degree requiring an additional fourth
year). Almost concurrently the extensive and relatively heavy monograph
of Hill [20] appeared which became a leading text for many years. Thereafter, of course, more and more monographs were published, like the very
readable second text of Hill [21] and the book of Rushbrooke [38], and today
a large number of pedagogically arranged texts is available. Thus the author himself taught the subject repeatedly on the basis of the more extensive
of the two widely known books of Reif [35], [36] together with some thermodynamics from Callen [6]. However later, motivated by the introduction
of Bachelor degree courses in Germany, the author reconsulted the lecture
notes he took in the course of Professor R.B. Dingle at the University of
Western Australia in 1956, and realized that this course covered in a clear
and logically arranged way the vital basic points of the subject and included
a large number of illustrating examples and exercises (in the present text
most of the examples with solutions). The following text is a presentation
ix

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PREFACE

of the subject arranged along the lines of this course for which the author is
indebted to his former teacher who, it may be pointed out here, made significant contributions to the subject, particularly in providing the first valid
demonstrations of BoseEinstein condensation (in an ideal gas). This introduction to Statistical Physics, which took the authors notes of this course as
a guide-line and employs only wave mechanics instead of full operator quantum mechanics, may be of interest to others who are interested in a Bachelor
Degree course, or equivalent introductory course to the subject, though, of
course, supplemented by some additions (apart from the introduction, particularly the section on BoseEinstein condensation and the problems without
worked solutions) and slight expansion throughout. The reader may ask,
however, how this text which is meant to be a first introduction to the
subject differs from other texts on the subject. One answer may be that
the central issues here are clearly separated from applications classical
versus quantum physics, a priori probability and degeneracy, distinguishability and indistinguishability, differences between conserved and nonconserved
elements, differences in counting of arrangements in the various statistics,
and maximization versus averaging of these. In particular the text proceeds
stepwise to the ultimate DarwinFowler method of mean values which not
only yields exact results but also provides the basis for the rigorous proof
of BoseEinstein condensation as given by Dingle. Applications are mostly
relegated to examples. It will be evident from the text that the author also
consulted a number of modern and recent monographs on the subject, and
compared the treatment in these with that here, also to provide references
with further details. For the convenience of students calculations are generally given in detail.
Harald J.W. M
ullerKirsten