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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
125 London Wall, London EC2Y 5AS, United Kingdom
525 B Street, Suite 1650, San Diego, CA 92101, United States
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The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
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
publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our
arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be
found at our website: www.elsevier.com/permissions.
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.
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"Not one bit!" said Amice, with emphasis.
"That may be all so, but what does it amount to, after all?"
said Amice. "Look at that same Mother Mary Monica. She
has been a nun in this and the other house sixty years, and
what have those sixty years brought to pass? What has she
to show for them?"
"And the sweetmeats are eaten, and the cordials drank, and
in a few years the embroidery—what remains of it—will be
rags and dust! Old Dame Lee in the village has ten sons,
and I know not how many grandsons and daughters, all
good and useful folk."
"And Roger Smith has a dozen children, each one more
useless and idle than the other," said I.
"Even that same need which makes the old wife to trot,
chick! I must see my Lord before he goes abroad,
concerning certain leases and the like. It is through no good
will of mine, I promise thee, for I was never fond either of
Court or city in my best days, and now—But how goes it
with you, child?" he asked, interrupting himself. "Methinks
you are thin and pale."
I told him of my cold, and how I had taken it. I could see he
was pleased, though he bade me be careful of my health.
"I feel sure of it," said I; and then I reminded him how
devout and humble dear mother was—how careful of all
those under her government, and how exact in training
them to ways of devotion and truth; and I repeated to him
sundry verses of the Psalms, on which I had been thinking a
great deal of late.
"I remember them well," said she. "They came from Rome,
and have the blessing of our Holy Father the Pope. Did your
mother use them?"
"Surely, child! 'Tis the duty of all wives. The trouble was in
her being a wife at all, since she forsook a higher vocation
to become one. Nobody can deny that the vocation of a
religious is far higher than that of a wife."
"'A good religious will have nothing which she calls her
own,'" said Amice, as if quoting something. "She will strive
for perfection, and to acquire that she must be wholly
detached from all human affections, so that mother or child,
husband or brother, shall be no more to her than the rest of
the world. Are we not expressly told in the lives of the
Saints that St. Francis disregarded the remonstrances and
the curses of his father, and that even the tears and prayers
of his mother were nothing to him? Did not St. Clare, our
blessed founder, fly from her father's house at midnight,
and by the advice of St. Francis himself, conceal the step
she was about to take from her father and mother, and did
not St. Agnes herself shortly do the same, and absolutely
refuse to return, though she was but fourteen years old?"
"I will ask Mother Gertrude about it," said I; and the good
Mother entering at that moment, I laid the case before her.
She smiled rather sadly, methought, and looked lovingly at
the little curl of baby hair, as it lay on her hand.
"So you think it is not right for you to keep these things?"
said she.
"You! No, child, thank you all the same, not till you learn
the use of your fingers better than you have it now."
"But, dear Mother, I dare say the manuscript can wait," said
I. "There is no hurry, I know, for Father Fabian told me I
might take my time about it, and I can do it at one time as
well as another, even by lamplight; when I cannot work, I
can help about the copes, part of the day, or until they are
finished."
"I know it," answered Amice. "I ought to have knelt at her
feet and thanked her for her reproof, instead of feeling hurt.
I have lost a chance for exercising holy humility. I can go
down to the sacristy and do it when you meet her there."
"I'll tell you a better way," said I. "Get a piece of linen and
set yourself to work in earnest to practise the stitches, so
that you can help her another time; for you know, dear, you
really don't work very neatly, because you won't keep your
mind on your work. You are always wool-gathering—maybe
I should say meditating—about something else. Come now,
that will be the best way. I am sure Mother will be willing to
have me teach you, or to show you herself."
"What a pity!" said the Sacristine. "Do you think you could
mend it, Rosamond? There is not such another—no, not at
Glastonbury itself, Father Fabian says."
"I can try!" said I. "If I fail, there will be no great loss."
CHAPTER VI.
May 15th.
We have been mighty busy all day preparing for the feast
to-morrow. We are to have high mass, and the celebrant is
none other than my Lord Bishop himself, who thus honors
our poor family. He has been here to-day, and has had long
conference with Mother Superior, Father Fabian and the
other elders. I fancy the two first wear a shade of care, and
even the Bishop does not look as easy and merry as when I
have seen him before.
CHAPTER VII.
St. John Baptist's Day, June 24.
"Do not be fluttered," said he, kindly. "Take time, and tell
me what you think."
As I came out from the parlor into the passage, and from
thence to the cloister door, I saw Sister Catherine and Sister
Mary Paula whispering together. They stopped talking when
I came out, and looked eagerly towards me.
With that, before I could hinder, she knelt down and kissed
my feet, and walked away, looking, I am sure, anything but
humble. I don't see either why one should rejoice in being
despised, since 'tis a wicked thing to despise people.
[I know now, what I did not then, that our house was
threatened with total destruction. Not long before Cardinal
Wolsey had founded his college at Oxford, and he had
obtained a bull from the Pope for suppressing some thirty of
the small religious houses and to endow his said college
with their revenues; and now there was talk of another
suppression. We have in our West country a pithy proverb
about showing the cat the way to the cream, which his
Eminence might have remembered, if he ever chanced to
hear it.]
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