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Statistical Mechanics
Statistical Mechanics
Fourth Edition
R.K. Pathria
Department of Physics
University of California San Diego
La Jolla, CA, United States
Paul D. Beale
Department of Physics
University of Colorado Boulder
Boulder, CO, United States
Academic Press is an imprint of Elsevier
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Copyright © 2022 Elsevier Ltd. All rights reserved.
Previous editions copyrighted 1972, 1996, 2011
No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical,
including photocopying, recording, or any information storage and retrieval system, without permission in writing from the
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This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may
be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and experience broaden our
understanding, changes in research methods, professional practices, or medical treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any
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To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any
injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or
operation of any methods, products, instructions, or ideas contained in the material herein.
ISBN: 978-0-08-102692-2
Cover: The image depicts a high-level wavefunction of a quantum Sinai billiard created using an algorithm by Kaufman et
al. (1999) and IDL software (Exelis Visual Information Solutions, Boulder, Colorado).
Problems 285
R.K.P.
P.D.B.
Preface to the third edition
The second edition of Statistical mechanics was published in 1996. The new material
added at that time focused on phase transitions, critical phenomena, and the renormal-
ization group – topics that had undergone vast transformations during the years following
the publication of the first edition in 1972. In 2009, R. K. Pathria (R.K.P.) and the publish-
ers agreed it was time for a third edition to incorporate the important changes that had
occurred in the field since the publication of the second edition and invited Paul D. Beale
(P.D.B.) to join as coauthor. The two authors agreed on the scope of the additions and
changes and P.D.B. wrote the first draft of the new sections except for Appendix F, which
was written by R.K.P. Both authors worked very closely together editing the drafts and fi-
nalizing this third edition.
The new topics added to this edition are:
• Bose–Einstein condensation and degenerate Fermi gas behavior in ultracold atomic
gases: Sections 7.2, 8.4, 11.2.A, and 11.9. The creation of Bose–Einstein condensates in
ultracold gases during the 1990s and in degenerate Fermi gases during the 2000s led
to a revolution in atomic, molecular, and optical physics, and provided a valuable link
to the quantum behavior of condensed matter systems. Several of P.D.B.’s friends and
colleagues in physics and JILA at the University of Colorado have been leaders in this
exciting new field.
• Finite-size scaling behavior of Bose–Einstein condensates: Appendix F. We develop an
analytical theory for the behavior of Bose–Einstein condensates in a finite system,
which provides a rigorous justification for singling out the ground state in the calcu-
lation of the properties of the Bose–Einstein condensate.
• Thermodynamics of the early universe: Chapter 9. The sequence of thermodynamic
transitions that the universe went through shortly after the Big Bang left behind mile-
posts that astrophysicists have exploited to look back into the universe’s earliest mo-
ments. Major advances in space-based astronomy beginning around 1990 have pro-
vided a vast body of observational data about the early evolution of the universe. These
include the Hubble Space Telescope’s deep space measurements of the expansion of
the universe, the Cosmic Background Explorer’s precise measurements of the temper-
ature of the cosmic microwave background, and the Wilkinson Microwave Anisotropy
Probe’s mapping of the angular variations in the cosmic microwave background. These
data sets have led to precise determinations of the age of the universe and its compo-
sition and early evolution. Coincidentally, P.D.B.’s faculty office is located in the tower
named after George Gamow, a member of the faculty at the University of Colorado in
the 1950s and 1960s and a leader in the theory of nucleosynthesis in the early universe.
xv
xvi Preface to the third edition
• Chemical equilibrium: Section 6.6. Chemical potentials determine the conditions nec-
essary for chemical equilibrium. This is an important topic in its own right, but also
plays a critical role in our discussion of the thermodynamics of the early universe in
Chapter 9.
• Monte Carlo and molecular dynamics simulations: Chapter 16. Computer simulations
have become an important tool in modern statistical mechanics. We provide here a
brief introduction to Monte Carlo and molecular dynamics techniques and algorithms.
• Correlation functions and scattering: Section 10.7. Correlation functions are central to
the understanding of thermodynamic phases, phase transitions, and critical phenom-
ena. The differences between thermodynamic phases are often most conspicuous in
the behavior of correlation functions and the closely related static structure factors. We
have collected discussions from the second edition into one place and added new ma-
terial.
• The fluctuation–dissipation theorem and the dynamical structure factor: Sections 15.3.A,
15.6.A, and 15.6.B. The fluctuation–dissipation theorem describes the relation be-
tween natural equilibrium thermodynamic fluctuations in a system and the response
of the system to small disturbances from equilibrium, and it is one of the corner-
stones of nonequilibrium statistical mechanics. We have expanded the discussion of
the fluctuation–dissipation theorem to include a derivation of the key results from lin-
ear response theory, a discussion of the dynamical structure factor, and analysis of the
Brownian motion of harmonic oscillators that provides useful practical examples.
• Phase equilibrium and the Clausius–Clapeyron equation: Sections 4.6 and 4.7. Much of
the text is devoted to using statistical mechanics methods to determine the properties
of thermodynamic phases and phase transitions. This brief overview of phase equilib-
rium and the structure of phase diagrams lays the groundwork for later discussions.
• Exact solutions of one-dimensional fluid models: Section 13.1. One-dimensional fluid
models with short-range interactions do not exhibit phase transitions but they do dis-
play short-range correlations and other behaviors typical of dense fluids.
• Exact solution of the two-dimensional Ising model on a finite lattice: Section 13.4.A. This
solution entails an exact counting of the microstates of the microcanonical ensemble
and provides analytical results for the energy distribution, internal energy, and heat
capacity of the system. This solution also describes the finite-size scaling behavior of
the Ising model near the transition point and provides an exact framework that can be
used to test Monte Carlo methods.
• Summary of thermodynamic assemblies and associated statistical ensembles: Appen-
dix H. We provide a summary of thermodynamic relations and their connections to
statistical mechanical ensembles. Most of this information can be found elsewhere in
the text, but we thought it would be helpful to provide a rundown of these important
connections in one place.
• Pseudorandom number generators: Appendix I. Pseudorandom number generators are
indispensable in computer simulations. We provide simple algorithms for generating
uniform and Gaussian pseudorandom numbers and discuss their properties.
• Dozens of new homework problems.
Preface to the third edition xvii
R.K.P.
P.D.B.
Preface to the second edition
The first edition of this book was prepared over the years 1966 to 1970, when the subject of
phase transitions was undergoing a complete overhaul. The concepts of scaling and uni-
versality had just taken root, but the renormalization group approach, which converted
these concepts into a calculational tool, was still obscure. Not surprisingly, my text of that
time could not do justice to these emerging developments. Over the intervening years I
have felt increasingly conscious of this rather serious deficiency in the text; so when the
time came to prepare a new edition, my major effort went toward correcting that defi-
ciency.
Despite the aforementioned shortcoming, the first edition of this book has continued
to be popular since its original publication in 1972. I, therefore, decided not to tinker with
it unnecessarily. Nevertheless, to make room for the new material, I had to remove some
sections from the present text, which, I felt, were not being used by the readers as much as
the rest of the book was. This may turn out to be a disappointment to some individuals but
I trust they will understand the logic behind it and, if need be, I will go back to a copy of the
first edition for reference. I, on my part, hope that a good majority of the users will not be
inconvenienced by these deletions. As for the material retained, I have confined myself to
making only editorial changes. The subject of phase transitions and critical phenomena,
which has been my main focus of revision, has been treated in three new chapters that
provide a respectable coverage of the subject and essentially bring the book up to date.
These chapters, along with a collection of more than 60 homework problems, will, I believe,
enhance the usefulness of the book for both students and instructors.
The completion of this task has left me indebted to many. First of all, as mentioned in
the preface to the first edition, I owe a considerable debt to those who have written on this
subject before and from whose writings I have benefited greatly. It is difficult to thank them
all individually; the bibliography at the end of the book is an obvious tribute to them. As for
definitive help, I am most grateful to Dr. Surjit Singh, who advised me expertly and assisted
me generously in the selection of the material that comprises Chapters 11 to 13 of the new
text; without his help, the final product might not have been as coherent as it now appears
to be. On the technical side, I am very thankful to Mrs. Debbie Guenther, who typed the
manuscript with exceptional skill and proofread it with extreme care; her task was clearly
an arduous one but she performed it with good cheer – for which I admire her greatly.
Finally, I wish to express my heartfelt appreciation for my wife, who let me devote
myself fully to this task over a rather long period of time and waited for its completion
ungrudgingly.
R.K.P.
xix
Preface to the first edition
This book has arisen out of the notes of lectures that I gave to the graduate students at
McMaster University (1964–1965), the University of Alberta (1965–1967), the University of
Waterloo (1969–1971), and the University of Windsor (1970–1971). While the subject mat-
ter, in its finer details, has changed considerably during the preparation of the manuscript,
the style of presentation remains the same as followed in these lectures.
Statistical mechanics is an indispensable tool for studying physical properties of
matter “in bulk” on the basis of the dynamical behavior of its “microscopic” constituents.
Founded on the well-laid principles of mathematical statistics on the one hand and Hamil-
tonian mechanics on the other, the formalism of statistical mechanics has proved to be of
immense value to the physics of the last 100 years. In view of the universality of its appeal,
a basic knowledge of this subject is considered essential for every student of physics, ir-
respective of the area(s) in which he/she may be planning to specialize. To provide this
knowledge, in a manner that brings out the essence of the subject with due rigor but with-
out undue pain, is the main purpose of this work.
The fact that the dynamics of a physical system is represented by a set of quantum states
and the assertion that the thermodynamics of the system is determined by the multiplicity
of these states constitute the basis of our treatment. The fundamental connection between
the microscopic and the macroscopic descriptions of a system is uncovered by investi-
gating the conditions for equilibrium between two physical systems in thermodynamic
contact. This is best accomplished by working in the spirit of the quantum theory right
from the beginning; the entropy and other thermodynamic variables of the system then
follow in a most natural manner. After the formalism is developed, one may (if the situa-
tion permits) go over to the limit of the classical statistics. This message may not be new,
but here I have tried to follow it as far as is reasonably possible in a textbook. In doing so, an
attempt has been made to keep the level of presentation fairly uniform so that the reader
does not encounter fluctuations of too wild a character.
This text is confined to the study of the equilibrium states of physical systems and is
intended to be used for a graduate course in statistical mechanics. Within these bounds,
the coverage is fairly wide and provides enough material for tailoring a good two-semester
course. The final choice always rests with the individual instructor; I, for one, regard Chap-
ters 1 to 9 (minus a few sections from these chapters plus a few sections from Chapter 13)
as the “essential part” of such a course. The contents of Chapters 10 to 12 are relatively
advanced (not necessarily difficult); the choice of material out of these chapters will de-
pend entirely on the taste of the instructor. To facilitate the understanding of the subject,
the text has been illustrated with a large number of graphs; to assess the understanding, a
large number of problems have been included. I hope these features are found useful.
xxi
xxii Preface to the first edition
I feel that one of the most essential aspects of teaching is to arouse the curiosity of the
students in their subject, and one of the most effective ways of doing this is to discuss with
them (in a reasonable measure, of course) the circumstances that led to the emergence
of the subject. One would, therefore, like to stop occasionally to reflect upon the manner
in which the various developments really came about; at the same time, one may not like
the flow of the text to be hampered by the discontinuities arising from an intermittent
addition of historical material. Accordingly, I decided to include in this account a historical
introduction to the subject which stands separate from the main text. I trust the readers,
especially the instructors, will find it of interest.
For those who wish to continue their study of statistical mechanics beyond the confines
of this book, a fairly extensive bibliography is included. It contains a variety of references
– old as well as new, experimental as well as theoretical, technical as well as pedagogical. I
hope that this will make the book useful for a wider readership.
The completion of this task has left me indebted to many. Like most authors, I owe con-
siderable debt to those who have written on the subject before. The bibliography at the
end of the book is the most obvious tribute to them; nevertheless, I would like to mention,
in particular, the works of the Ehrenfests, Fowler, Guggenheim, Schrödinger, Rushbrooke,
ter Haar, Hill, Landau and Lifshitz, Huang, and Kubo, who have been my constant refer-
ence for several years and have influenced my understanding of the subject in a variety of
ways. As for the preparation of the text, I am indebted to Robert Teshima, who drew most
of the graphs and checked most of the problems, to Ravindar Bansal, Vishwa Mittar, and
Surjit Singh, who went through the entire manuscript and made several suggestions that
helped me unkink the exposition at a number of points, to Mary Annetts, who typed the
manuscript with exceptional patience, diligence, and care, and to Fred Hetzel, Jim Briante,
and Larry Kry, who provided technical help during the preparation of the final version.
As this work progressed I felt increasingly gratified toward Professors F. C. Auluck and
D. S. Kothari of the University of Delhi, with whom I started my career and who initiated
me into the study of this subject, and toward Professor R. C. Majumdar, who took keen
interest in my work on this and every other project that I have undertaken from time to
time. I am grateful to Dr. D. ter Haar, of the University of Oxford, who, as the general editor
of this series, gave valuable advice on various aspects of the preparation of the manuscript
and made several useful suggestions toward the improvement of the text. I am thankful to
Professors J. W. Leech, J. Grindlay, and A. D. Singh Nagi of the University of Waterloo for
their interest and hospitality that went a long way in making this task a pleasant one.
The final tribute must go to my wife, whose cooperation and understanding, at all
stages of this project and against all odds, have been simply overwhelming.
R.K.P.
Historical introduction
Statistical mechanics is a formalism that aims at explaining the physical properties of mat-
ter in bulk on the basis of the dynamical behavior of its microscopic constituents. The
scope of the formalism is almost as unlimited as the very range of the natural phenomena,
for in principle it is applicable to matter in any state whatsoever. It has, in fact, been ap-
plied, with considerable success, to the study of matter in the solid state, the liquid state, or
the gaseous state, matter composed of several phases and/or several components, matter
under extreme conditions of density and temperature, matter in equilibrium with radia-
tion (as, for example, in astrophysics), matter in the form of a biological specimen, and
so on. Furthermore, the formalism of statistical mechanics enables us to investigate the
nonequilibrium states of matter as well as the equilibrium states; indeed, these investiga-
tions help us to understand the manner in which a physical system that happens to be “out
of equilibrium” at a given time t approaches a “state of equilibrium” as time passes.
In contrast with the present status of its development, the success of its applications,
and the breadth of its scope, the beginnings of statistical mechanics were rather modest.
Barring certain primitive references, such as those of Gassendi, Hooke, and so on, the real
work on this subject started with the contemplations of Bernoulli (1738), Herapath (1821),
and Joule (1851), who, in their own individual ways, attempted to lay a foundation for the
so-called kinetic theory of gases – a discipline that finally turned out to be the forerunner
of statistical mechanics. The pioneering work of these investigators established the fact
that the pressure of a gas arose from the motion of its molecules and could, therefore, be
computed by considering the dynamical influence of the molecular bombardment on the
walls of the container. Thus, Bernoulli and Herapath could show that, if the temperature
remained constant, the pressure P of an ordinary gas was inversely proportional to the vol-
ume V of the container (Boyle’s law), and that it was essentially independent of the shape
of the container. This, of course, involved the explicit assumption that, at a given tempera-
ture T , the (mean) speed of the molecules was independent of both pressure and volume.
Bernoulli even attempted to determine the (first-order) correction to this law, arising from
the finite size of the molecules, and showed that the volume V appearing in the statement
of the law should be replaced by (V − b), where b is the “actual” volume of the molecules.1
Joule was the first to show that the pressure P was directly proportional to the square
of the molecular speed c, which he had initially assumed to be the same for all molecules.
Krönig (1856) went a step further. Introducing the “quasistatistical” assumption that, at
any time t, one-sixth of the molecules could be assumed to be flying in each of the six
1
As is well known, this “correction” was correctly evaluated, much later, by van der Waals (1873), who showed
that, for large V , b is four times the “actual” volume of the molecules; see Problem 1.4.
xxiii
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from Cluny. Fifty years later three Cluniac monks were sent over to
set forth the claims of the Mother House. The brethren stated their
case, but could not get any attention paid to their arguments. One
of them died in this country, the other two went home having
accomplished nothing. A piteous letter to the Abbot of St. Albans
explains their position:—
“For the rest, be it known to you, my Lord, that after having spent
four months and a half on our journey, and following our Right with
the most serene Lord the King and his Privy Council, we have
obtained nothing: nay, we are sent back very disconsolate, deprived
of our Manors, our Pensions alienated, and what is still worse, we
are denied the obedience of all our Monasteries which are 38 in
number: nor did our Legal Deeds, nor the Testimonies of your
Chronicles avail us anything, and at length, after all our pleading and
expenses, we return home moneyless, for in truth, after paying for
what we have eaten and drunk, we have but five crowns left, to go
back about 260 leagues. But what then? We will sell what we have;
we will go on; and God will provide. Nothing else occurs to write to
your Paternity: but that as we entered England with joy, so we
depart thence with sorrow; having buried one of our Companions—
viz. the Archdeacon, the youngest of our company. May he rest in
Peace! Amen.”
THE ARMS AND SEALS OF THE PRIOR AND CONVENT OF ST. SAVIOUR
AT BERMONDSEY
W. B. Grove.
“It is now called, The new Chappell; and indeed, though very
old, it now may be cal’d a new one, because newly redeemed
from such use and imployment, as in respect of that it was built
to, Divine and Religious duties, may very well be branded, with
the stile of wretched, base, and unworthy, for that before this
abuse, was (and is now) a faire & beautifull Chappell, by those
that were then the Corporation (which is a body consisting of
30. Vestry men, sixe of those thirty, Churchwardens) was leased
and let out, and this House of God made a Bake-house.
Two very faire doores, that from the two side Iles of the
Chancell of this Church, and two that throw the head of the
Chancell (as at this day they doe againe) went into it, were
lath’t, daub’d, and dam’d up: the faire Pillars were ordinary
posts, against which they piled Billets and Bavens; in this place
they had their Ovens, in that a Bolting-place, in that their
Kneading-trough, in another (I have heard) a Hogs-trough; for
the words that were given mee were these, This place have I
knowne a Hog-stie, in another a Store-house, to store up their
hoorded Meale: and in all of it, something of this sordid kind &
condition.
It was first let by the Corporation afore named, to one Wyat,
after him to one Peacocke, after him to one Cleybrooke, and last
to one Wilson, all Bakers, and this Chappell still imployed in the
way of their Trade, a Bake-house, though some part of this
Bake-house was sometime turned into a Starch-house.
The time of the continuance of it in this kind, from the first
letting of it to Wyat, to the restoring of it againe to the Church;
was threescore and some odde yeeres, in the yeere of our Lord
God 1624, for in this yeere the ruines and blasted estate that
the old Corporation sold it to, were by the Corporation of this
time repaired, renewed, well, and very worthily beautified; the
charge of it for that yeere, with many things done to it since,
arising to two hundred pounds.
This, as all the former Repaires, being the sole cost and
charge of the Parishioners.
One Ile in this Chappel, was paved at the onely cost of one
Master John Hayman, Taylor, and Merchantaylor, in the yeere
1625.”
GATEWAY OF ST. MARY’S PRIORY, SOUTHWARK
Londina Illustrata, vol. i.
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