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Frigg and Werndl
Statistical mechanics is the third pillar of modern physics, next
to quantum theory and relativity theory. It aims to account
for the behaviour of macroscopic systems in terms of the
dynamical laws that govern their microscopic constituents
and probabilistic assumptions about them. In this Element, the
authors investigate the philosophical and foundational issues Philosophy of Physics
that arise in SM. The authors introduce the two main theoretical
approaches, Boltzmannian statistical mechanics and Gibbsian
statistical mechanics, and discuss how they conceptualise
equilibrium and explain the approach to it. In doing so, the
authors examine how probabilities are introduced into the
theories, how they deal with irreversibility, how they understand
of Statistical
of future research. This title is also available as Open Access on
Cambridge Core.
FOUNDATIONS OF
STATISTICAL MECHANICS
Roman Frigg
The London School of Economics and Political Science
Charlotte Werndl
University of Salzburg
Shaftesbury Road, Cambridge CB2 8EA, United Kingdom
One Liberty Plaza, 20th Floor, New York, NY 10006, USA
477 Williamstown Road, Port Melbourne, VIC 3207, Australia
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103 Penang Road, #05–06/07, Visioncrest Commercial, Singapore 238467
www.cambridge.org
Information on this title: www.cambridge.org/9781009468237
DOI: 10.1017/9781009022798
© Roman Frigg and Charlotte Werndl 2023
This work is in copyright. It is subject to statutory exceptions and to the provisions
of relevant licensing agreements; with the exception of the Creative Commons version
the link for which is provided below, no reproduction of any part of this work may take
place without the written permission of Cambridge University Press & Assessment.
An online version of this work is published at doi.org/10.1017/9781009022798 under
a Creative Commons Open Access license CC-BY-NC 4.0 which permits re-use,
distribution and reproduction in any medium for non-commercial purposes providing
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To view a copy of this license visit https://creativecommons.org/licenses/by-nc/4.0.
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parties directly.
When citing this work, please include a reference to the DOI 10.1017/9781009022798.
First published 2023
A catalogue record for this publication is available from the British Library.
ISBN 978-1-009-46823-7 Hardback
ISBN 978-1-009-01649-0 Paperback
ISSN 2632-413X (online)
ISSN 2632-4121 (print)
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publication and does not guarantee that any content on such websites is, or will
remain, accurate or appropriate.
Foundations of Statistical Mechanics
DOI: 10.1017/9781009022798
First published online: December 2023
Roman Frigg
The London School of Economics and Political Science
Charlotte Werndl
University of Salzburg
Author for correspondence: Charlotte Werndl, charlotte.werndl@sbg.ac.at
1 Introduction 1
References 67
Foundations of Statistical Mechanics 1
1 Introduction
1.1 The Aims of Statistical Mechanics
Statistical mechanics (SM) is the third pillar of modern physics, next to
quantum theory and relativity theory. Its aim is to account for the behaviour
of macroscopic systems in terms of the dynamical laws that govern their
microscopic constituents and probabilistic assumptions about them. The use
of probabilities is motivated by the fact that systems studied by SM have
a large number of microscopic constituents. Paradigmatic examples of sys-
tems studied in SM are gases, liquids, crystals, and magnets, which all have
a number of microscopic constituents that is of the order of Avogadro’s
number (6.022 × 1023).1
The focal point of SM is a particular aspect of the behaviour of macro-
systems, namely equilibrium. To introduce equilibrium, and to boost intu-
itions, let us consider a standard example. A gas is confined to the left half of
a container with a dividing wall, as illustrated in Figure 1a. The gas is in
equilibrium in the sense that there is no manifest change in any of its macro
properties like pressure, temperature, and volume, and the gas will have these
macro properties so long as the container remains unchanged. Now consider
such a change: remove the dividing wall in the middle, as illustrated in
Figure 1b. The gas is now no longer in equilibrium because it does not fill
the container evenly. As a result, the gas starts spreading through the entire
available volume, as illustrated in Figure 1c. The spreading of the gas comes to
an end when the entire container is filled evenly and no further change takes
place, as illustrated in Figure 1d. At this point, the gas has reached a new
equilibrium. Since the process of spreading culminates in a new equilibrium,
this process is an approach to equilibrium. A key characteristic of the
approach to equilibrium is that it seems to be irreversible: systems move
from non-equilibrium to equilibrium, but not vice versa: gases spread to fill
the container evenly, but they do not spontaneously concentrate in the left half
of the container. Since an irreversible approach to equilibrium is often associ-
ated with thermodynamics, this is referred to as thermodynamic behaviour.2
1
From now on, we will use ‘micro’ and ‘macro’ as synonyms for ‘microscopic’ and ‘macroscopic’,
and we will speak of macro systems and their micro constituents, as well as of macro or micro
properties, macro or micro characterisations, and so on. We will also use ‘micro-states’ and
‘macro-states’, where we add the hyphen to indicate that they are unbreakable technical terms. We
use ‘SM systems’ as a shorthand for ‘the systems studied in SM’.
2
This is commonly seen as a result of the second law of thermodynamics. However, as Brown and
Uffink (2001) note, the irreversibility of the kind illustrated in our example is not part of
the second law and has to be added as an independent principle to the theory, which they call
the minus-first law.
2 Philosophy of Physics
Characterising the state of equilibrium and accounting for why, and how,
a system approaches equilibrium are the core tasks for SM. Sometimes these
two problems are assigned to separate parts of SM, namely equilibrium SM
and non-equilibrium SM.
What does characterising the state of equilibrium involve? We said that the
gas is in equilibrium when there is no manifest change in any of its macro
properties. This is a valid macro characterisation. Yet if the aim of SM is to
account for the macro properties of a system in terms of the behaviour of its
micro constituents, then we need a characterisation of equilibrium in micro-
physical terms: what condition does the motion of the molecules in a gas have to
satisfy for the gas to be in equilibrium? And how do the values of macroscopic
properties like local pressure and local temperature depend on the state of
motion of gas molecules? Equilibrium SM provides answers to these and related
questions.
Turning to non-equilibrium, the core question is how the tendency of systems
to move to equilibrium when prepared in a non-equilibrium state is grounded
in the dynamics of the micro constituents of the system: what is it about the
motions of molecules that leads them to spread so that the gas assumes a new
equilibrium state when the shutter is removed? And, crucially, what accounts
for the fact that the reverse process does not happen?
Foundations of Statistical Mechanics 3
This Element focuses on these questions. This, however, is not to say that SM
deals solely with equilibrium. While equilibrium occupies centre stage, SM also
addresses other issues such as phase transitions, the entropy costs of computa-
tion, and the process of mixing substances; and in philosophical contexts SM
has been employed to shed light on issues like the direction of time and the
possibility of knowledge about the past. Space constraints prevent us from
delving into these issues, and we will concentrate on equilibrium.
3
For reviews of these approaches see Frigg (2008b), Penrose (1970), Shenker (2017a, 2017b),
Sklar (1993), and Uffink (2007).
4
There is an interesting historical question about the origin and subsequent evolution of this
schism. We cannot discuss this question here, but we speculate that it goes back to Ehrenfest
and Ehrenfest-Afanassjewa’s seminal review (1912/1959). While they do not use the labels BSM
and GSM, they clearly separate a discussion of Boltzmann’s ideas, which they discuss under the
heading of ‘The Modern Formulation of Statistico-Mechanical Investigations’, and Gibbs’
contributions, which they discuss in a section entitled ‘W. Gibbs’s Elementary Principles in
Statistical Mechanics’.
4 Philosophy of Physics
1.3 Outline
In this Element we discuss how BSM and GSM deal with the questions
introduced in Section 1.1. Both BSM and GSM are formulated against the
background of dynamical systems theory and probability theory. In Section 2
we introduce the basic concepts of both theories and state results that are
important in the context of SM. In Section 3 we turn to BSM. We start by
introducing the core concepts of BSM and then discuss different ways of
developing them. Section 4 is dedicated to GSM. After introducing the formal-
ism, we discuss its interpretation and different developments, and we end by
considering the relation between BSM and GSM.
It goes without saying that omissions are inevitable. Some of them we have
already announced in Section 1.1: we focus on equilibrium and the approach
to it, and we set aside topics like phase transitions and the entropy costs of
computation, and we will only briefly touch on questions concerning
reductionism.6 In addition to these, we set aside approaches to SM that do not
clearly fall under the umbrella of either BSM or GSM, which implies that we do
not discuss the Boltzmann equation.7
8
For a discussion of foundational issues in quantum SM see, for instance, Emch (2007).
9
Our characterisation of a dynamical system is intuitive. For mathematical discussions see, for
instance, Arnold and Avez (1968) and Katok and Hasselblatt (1995).
6 Philosophy of Physics
three degrees of freedom. This means that a specification of the position of the
molecule requires three parameters, one for each spatial direction. Since the
molecule has a momentum in each direction, a further three parameters are
needed to specify its momentum. So we need six parameters to specify the state
of motion of a molecule. Accordingly, the specification of the state of the entire
gas with n molecules requires 6n parameters. Hence, X is a 6n-dimensional
space containing the positions and momenta of all molecules.
The second element of a dynamical system, t , is the time evolution function.
This function specifies how the state of a system changes over time, and we write
t ðxÞ to denote the state into which an initial state x evolves after time t. If the
time evolution is specified by equations of motion like Newton’s, Lagrange’s, or
Hamilton’s, then t ðxÞ is the solution of that equation (we discuss Hamilton’s
equations in more detail in the next section). As time passes, t ðxÞ draws a ‘line’
through X that represents the time evolution of a system that was initially in
state x; this ‘line’ is called a trajectory. This is illustrated in Figure 1.
The third element of a dynamical system, μ, is a measure on X. At a general
level, a measure is a device to attribute a size to an object. Familiar examples are
the attribution of a length to a segment of a line, a surface to a part of a plane, and
a volume to a portion of space. From a mathematical point of view X is a set, and
the measure μ attributes a ‘size’ – or ‘measure’ – to subsets of X in much the
same way in which a ruler attributes a length to, say, a pencil. If the measure μ is
able to attribute a size to a particular subset A ⊆ X , then A is said to be
measurable. In what follows we assume that all sets are measurable. If
a measure is such that μðX Þ ¼ 1, then the measure is normalised.
Things can be measured in different ways. One measure is of particular
importance in the current context: the so-called uniform Lebesgue measure.
This measure is a mathematically precise rendering of the measure we use when
attributing lengths and surfaces to objects. For instance, the interval [2, 5] has
uniform Lebesgue measure (or length) 3, and a circle with radius r has uniform
Lebesgue measure (or surface) of πr2 .
Foundations of Statistical Mechanics 7
∂H ∂H
q_ k ¼ and p_ k ¼ ;
∂pk ∂qk
where the dot indicates a derivative with respect to time and the index k ranges
over all degrees of freedom (so, for a gas we have k = 1, . . ., 3n). This defines
a system of k differential equations, and the solution to this equation is the time
evolution function t of the system. Solving these equations for SM systems is
usually a practical impossibility, and so we will not be able to write down t
explicitly. This does not render Hamiltonian mechanics useless. In fact, the
equations ensure that t has a number of general features, and these can be
10
For a brief introduction see, for instance, Argyris, Faust, and Haase (1994, ch. 4).
8 Philosophy of Physics
11
It is a hypersurface because ‘surface’ has the connotation of being two-dimensional, like
a tabletop, which the surface of constant energy is not.
Foundations of Statistical Mechanics 9
ð2Þ
evolutions like t are common in other contexts, and they are allowed, for
instance, if the guiding equation is Newton’s rather than Hamilton’s.
Before moving on, we briefly note that even though Hamiltonian mechanics is
assumed to be the fundamental theory of SM systems, in practical calculations
other dynamical laws are sometimes considered. Typical examples are the Kac ring
or the baker’s gas.12 These dynamical laws are typically chosen for two reasons:
they are simple and can be implemented relatively easily on computers, and yet
they share important features with the full Hamiltonian dynamics, most notably
measure preservation. So, even when considerations are made with alternative
dynamical laws, Hamiltonian mechanics informs and guides the choice.
12
For a discussion of the Kac ring, see Jebeile (2020); for the baker’s gas, see Lavis (2008).
13
In what follows we restrict attention to autonomous Hamiltonian systems.
14
Note that time-reversal invariance does not imply that processes must be such that they look the
same in both temporal directions: processes do not have to be palindromic. In our example, you
see a ball moving from left to right in one temporal direction and from right to left in the other.
For detailed discussions of time-reversal invariance see, for instance, Roberts (2022) and Uffink
(2001).
Foundations of Statistical Mechanics 11
coordinates q and p. When we stop the movie and start playing it backwards, the
position of the ball remains unchanged, but its momentum flips from p to p.
So, the time-reversed state of ðq; pÞ is ðq; pÞ. Hence, performing a so-called
time-reversal transformation amounts to replacing t by t and p by p.
In Hamiltonian mechanics the verdict on whether a process is allowed is cast
by the Hamiltonian equations of motion: if a process satisfies the equations, it is
allowed, and if not, it is ruled out. So, let us see how the Hamiltonian equations
behave under a time-reversal transformation. Some elementary algebraic
manipulations show that the equations are left unchanged if you replace t by
t and p by p. This means that processes unfolding backward in time are
governed by the same equation as those unfolding forward in time, and this
means that the theory – the Hamiltonian equations – cast the same verdict about
what is allowed in both directions of time. Hence, Hamiltonian mechanics is
time-reversal invariant. This means that if a process from an initial state ðqi ; pi Þ
to a final state ðqf ; pf Þ during timespan Δt is allowed, then a process starting in
state ðqf ; pf Þ and ending in ðqi ; pi Þ during timespan Δt is allowed too. As we
will see, this is the crucial formal ingredient of what is now known as
Loschmidt’s reversibility objection.
15
For a discussion of Poincaré recurrence, see, for instance, Cornfeld, Fomin, and Sinai (1982).
12 Philosophy of Physics
2.5 Ergodicity
Among the many properties that a time evolution can have, ergodicity is of
particular importance because it plays a crucial role in discussions of both BSM
and GSM.16 Consider a function f : X → ℂ, where ‘ℂ’ denotes the complex
numbers. Sometimes such a function is called a ‘phase function’ because in the
context of Hamiltonian mechanics X is also referred to as the phase space
(Section 2.2). The space average f of f (sometimes also called ‘phase average’,
for the same reasons) is
ð
f ¼ f dx: ð1Þ
x
16
For rigorous discussions of ergodicity and ergodic theory, see, for instance, Arnold and Avez
(1968), Cornfeld, Fomin, and Sinai (1982), and Petersen (1983).
Foundations of Statistical Mechanics 13
Figure 5 Ergodicity.
17
We can do this without loss of generality because, as we have seen, SM systems have a finite
phase space and one can then always choose the measure so that the entire space has measure
one.
14 Philosophy of Physics
[Contents]
D.—PENALTIES OF NEGLECT.
Both the effect and the cause of such excesses were rather rare in
the prime of the North American republic, when nearly every colonist
was a farmer, and every farm a polytechnicum of home-taught
trades; but European luxuries introduced European habits, and our
cities now abound with plutocrats who are ashamed of the toil by
which their forefathers laid the foundation of their wealth. Our cities
have bred the vices faster than the refinements of wealth, and have
become acquainted with ennui—
and thousands who would fail to find relief on the classical hunting-
grounds of Peter Bayle might imitate his landlord, who practiced
sharp-shooting with a medieval hunting-bow till he could challenge
the best pistol shots of the neighboring garrison. In a choice of evils
the most puerile game of skill is, indeed, clearly preferable to games
of chance; but [82]to that last resort of inanity the traditional aversion
to manual employments has actually driven thousands of city idlers.
Yet our American towns have never sunk to the abject effeminacy of
European cities, where physical apathy has become a test of good
breeding and a taste for mechanical accomplishments a stigma of
eccentricity, and where, consequently, social prestige has to be
purchased at the price of practical helplessness, of dependence in
all mechanical questions of life on the aid and the judgment of
hirelings.
[Contents]
E.—REFORM.
[Contents]
CHAPTER VI.
KNOWLEDGE.
[Contents]
A.—LESSONS OF INSTINCT.
In the arena of life animal instinct triumphs over the elemental forces
of Nature, as human intelligence triumphs over instinct, and the
secret of that superiority is knowledge. Skill is well-directed force.
Prudence is well-applied reason. The efficiency of that directing
faculty depends on experience, as we call the accumulation of
recollected facts. Knowledge is stored light, as helpful in the
narrowest as in the widest sphere of conscious activity, and the
instinctive appreciation of that advantage manifests itself in the
lowest species of vertebrate animals, nay, perhaps even in the
winged insects that swarm in from near and far to explore the
mystery of a flickering torch. Curiosity, rather than the supposed love
of rhythm, tempts the serpent to leave its den at the sound of the
conjurer’s flute. Dolphins are thus attracted by the din of a
kettledrum, river-fish by the glare of a moving light. Where deer
abound, a pitchwood fire, kindled in a moonless night, is sure to
allure them from all parts of the forest. Antelope hunters can entice
their game within rifle-shot by [86]fastening a red kerchief to a bush
and letting it flutter in the breeze. When the first telegraph lines
crossed the plateau of the Rocky Mountains, herds of bighorn sheep
were often seen trotting along the singing wires as if anxious to
ascertain the meaning of the curious innovation. Every abnormal
change in the features of a primitive landscape—the erection of a
lookout-tower, a clearing in the midst of a primeval forest—attracts
swarms of inquisitive birds, even crows and shy hawks, who seem to
recognize the advantage of reconnoitering the topography of their
hunting-grounds. In some of the higher animals inquisitiveness
becomes too marked to mistake its motive, as when a troop of colts
gathers about a new dog, or a pet monkey pokes his head into a
cellar-hole, and wears out his finger-nails to ascertain the contents of
a brass rattle.
The shrewd remarks of boy naturalists and girl satirists often almost
confirm the opinion of Goethe that every child has the innate gifts of
genius, and that subsequent differences are only the result of more
or less propitious educational influences. And in spite of most
discouraging circumstances, the love of knowledge sometimes
revives in after years with the energy almost of a passionate instinct.
On the veranda of a new hotel in a railroad town of southern Texas, I
once noticed the expression of rapt interest on the face of a young
hunter, a lad of eighteen or nineteen, who here for the first time
came in contact with the representatives of a higher civilization and
with breathless attention drank in the conversation of two far-traveled
strangers. “If they would hire me for a dog-robber (a low menial), I
would do it for a dime a day,” he muttered, “just for the chance to
hear them talk.”
“But if they should take you to some smoky, crowded, big city?”
“I don’t care,” said he, with an oath, “I would let them lock me up in a
jail, if I could get an education like theirs.”
[Contents]
B.—REWARDS OF CONFORMITY.
[Contents]
C.—PERVERSION.
When the tyranny of the church reached the zenith of its power,
natural science became almost a tradition of the past. The pedants
of the convent schools divided their time between the forgery of
miracle legends and the elaboration of insane dogmas. The most
extravagant absurdities were propagated under the name of
historical records; medleys of nursery-tales and ghost-stories which
the poorest village school-teacher of pagan Rome would have
rejected with disgust were gravely discussed by so-called scholars.
Buckle, in his “History of Civilization,” quotes samples of such
chronicles which might be mistaken for products of satire, if
abundant evidence of contemporary writers did not prove them to
have been the current staple of medieval science.
When the gloom of the dreadful night was broken by the first gleam
of modern science, every torch-bearer was persecuted as an
incendiary. Astronomers were forced to recant their heresies on their
bended knees. Philosophers were caged like wild beasts. Religious
skeptics were burnt at the stake, as [92]enemies of God and the
human race. It was, indeed, almost impossible to enunciate any
scientific axiom that did not conflict with the dogmas of the
revelation-mongers who had for centuries subordinated the evidence
of their own senses to the rant of epileptic monks and maniacs. And
when the sun of Reason rose visibly above the horizon of the
intellectual world, its rays struggled distorted through the dense mist
of superstition which continued to brood over the face of the earth,
and was only partially dispersed even by the storms of the Protestant
revolt.
The light of modern science has brought its blessings only to the
habitants of the social highlands; the valley dwellers still grope their
way through the gloom of inveterate superstitions and prejudices,
and centuries may pass before the world has entirely emerged from
the shadow of the life-blighting cloud which the son of Sospitra
recognized in the rise of the Galilean delusion.
[Contents]
D.—PENALTIES OF NEGLECT.
[Contents]
E.—REFORM.
The experience of the Middle Ages has made the separation of
church and state the watchword of all true Liberals. But the divorce
of church and school is a duty of hardly less urgent importance.
While many of our best Freethinkers waste their time in hair-splitting
metaphysics, Catholic and Protestant Jesuits coöperate for a
purpose which they have shrewdly recognized as the main hope of
obscurantism: The perversion of primary education by its re-
subjection to the control of the clergy. The definite defeat of those
intrigues should be considered the only permanent guarantee
against the revival of spiritual feudalism. A perhaps less imminent,
but hardly less serious, danger to the cause of Science is the
stealthy revival of mysticism. Under all sorts of nomenclatural
modifications, the specter-creed of the ancient Gnostics is again
rearing its head, and menacing reason by an appeal to the hysterical
and sensational proclivities of ignorance.
[Contents]
CHAPTER VII.
INDEPENDENCE.
[Contents]
A.—LESSONS OF INSTINCT.
[Contents]
B.—REWARDS OF CONFORMITY.
Since the dawn of history the lands of freedom have produced fruits
and flowers that refused to thrive on any other soil. For several
centuries civilization was confined to a small country of republics:
Attic and Theban Greece. “Study the wonders of that age,” says
Byron to his friend Trelawney, “and compare them with the best ever
done under masters.” Switzerland, in spite of its rocky soil, has for
centuries been the happiest, as well as the freest, country of Europe.
The prosperity of the United States of America, since the
establishment of their independence, stands unparalleled in the
history of the last eighteen hundred years; and, moreover, the
degree of that [99]prosperity has been locally proportioned to the
degree of social freedom, and has begun to become general only
since the general abolition of slavery. Freedom blesses the poorest
soil, as despotism blights the most fertile, and it is only an apparent