H-Theorem and Beyond: Boltzmann's Entropy in Today's Mathematics
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A Simple Method to Estimate Entropy and Free Energy of Atmospheric Gases from Their Action
Article A Simple Method to Estimate Entropy and Free Energy of Atmospheric Gases from Their Action Ivan Kennedy 1,2,*, Harold Geering 2, Michael Rose 3 and Angus Crossan 2 1 Sydney Institute of Agriculture, University of Sydney, NSW 2006, Australia 2 QuickTest Technologies, PO Box 6285 North Ryde, NSW 2113, Australia; [email protected] (H.G.); [email protected] (A.C.) 3 NSW Department of Primary Industries, Wollongbar NSW 2447, Australia; [email protected] * Correspondence: [email protected]; Tel.: + 61-4-0794-9622 Received: 23 March 2019; Accepted: 26 April 2019; Published: 1 May 2019 Abstract: A convenient practical model for accurately estimating the total entropy (ΣSi) of atmospheric gases based on physical action is proposed. This realistic approach is fully consistent with statistical mechanics, but reinterprets its partition functions as measures of translational, rotational, and vibrational action or quantum states, to estimate the entropy. With all kinds of molecular action expressed as logarithmic functions, the total heat required for warming a chemical system from 0 K (ΣSiT) to a given temperature and pressure can be computed, yielding results identical with published experimental third law values of entropy. All thermodynamic properties of gases including entropy, enthalpy, Gibbs energy, and Helmholtz energy are directly estimated using simple algorithms based on simple molecular and physical properties, without resource to tables of standard values; both free energies are measures of quantum field states and of minimal statistical degeneracy, decreasing with temperature and declining density. We propose that this more realistic approach has heuristic value for thermodynamic computation of atmospheric profiles, based on steady state heat flows equilibrating with gravity. -
Arxiv:1910.10745V1 [Cond-Mat.Str-El] 23 Oct 2019 2.2 Symmetry-Protected Time Crystals
A Brief History of Time Crystals Vedika Khemania,b,∗, Roderich Moessnerc, S. L. Sondhid aDepartment of Physics, Harvard University, Cambridge, Massachusetts 02138, USA bDepartment of Physics, Stanford University, Stanford, California 94305, USA cMax-Planck-Institut f¨urPhysik komplexer Systeme, 01187 Dresden, Germany dDepartment of Physics, Princeton University, Princeton, New Jersey 08544, USA Abstract The idea of breaking time-translation symmetry has fascinated humanity at least since ancient proposals of the per- petuum mobile. Unlike the breaking of other symmetries, such as spatial translation in a crystal or spin rotation in a magnet, time translation symmetry breaking (TTSB) has been tantalisingly elusive. We review this history up to recent developments which have shown that discrete TTSB does takes place in periodically driven (Floquet) systems in the presence of many-body localization (MBL). Such Floquet time-crystals represent a new paradigm in quantum statistical mechanics — that of an intrinsically out-of-equilibrium many-body phase of matter with no equilibrium counterpart. We include a compendium of the necessary background on the statistical mechanics of phase structure in many- body systems, before specializing to a detailed discussion of the nature, and diagnostics, of TTSB. In particular, we provide precise definitions that formalize the notion of a time-crystal as a stable, macroscopic, conservative clock — explaining both the need for a many-body system in the infinite volume limit, and for a lack of net energy absorption or dissipation. Our discussion emphasizes that TTSB in a time-crystal is accompanied by the breaking of a spatial symmetry — so that time-crystals exhibit a novel form of spatiotemporal order. -
LECTURES on MATHEMATICAL STATISTICAL MECHANICS S. Adams
ISSN 0070-7414 Sgr´ıbhinn´ıInstiti´uid Ard-L´einnBhaile´ Atha´ Cliath Sraith. A. Uimh 30 Communications of the Dublin Institute for Advanced Studies Series A (Theoretical Physics), No. 30 LECTURES ON MATHEMATICAL STATISTICAL MECHANICS By S. Adams DUBLIN Institi´uid Ard-L´einnBhaile´ Atha´ Cliath Dublin Institute for Advanced Studies 2006 Contents 1 Introduction 1 2 Ergodic theory 2 2.1 Microscopic dynamics and time averages . .2 2.2 Boltzmann's heuristics and ergodic hypothesis . .8 2.3 Formal Response: Birkhoff and von Neumann ergodic theories9 2.4 Microcanonical measure . 13 3 Entropy 16 3.1 Probabilistic view on Boltzmann's entropy . 16 3.2 Shannon's entropy . 17 4 The Gibbs ensembles 20 4.1 The canonical Gibbs ensemble . 20 4.2 The Gibbs paradox . 26 4.3 The grandcanonical ensemble . 27 4.4 The "orthodicity problem" . 31 5 The Thermodynamic limit 33 5.1 Definition . 33 5.2 Thermodynamic function: Free energy . 37 5.3 Equivalence of ensembles . 42 6 Gibbs measures 44 6.1 Definition . 44 6.2 The one-dimensional Ising model . 47 6.3 Symmetry and symmetry breaking . 51 6.4 The Ising ferromagnet in two dimensions . 52 6.5 Extreme Gibbs measures . 57 6.6 Uniqueness . 58 6.7 Ergodicity . 60 7 A variational characterisation of Gibbs measures 62 8 Large deviations theory 68 8.1 Motivation . 68 8.2 Definition . 70 8.3 Some results for Gibbs measures . 72 i 9 Models 73 9.1 Lattice Gases . 74 9.2 Magnetic Models . 75 9.3 Curie-Weiss model . 77 9.4 Continuous Ising model . -
Entropy and H Theorem the Mathematical Legacy of Ludwig Boltzmann
ENTROPY AND H THEOREM THE MATHEMATICAL LEGACY OF LUDWIG BOLTZMANN Cambridge/Newton Institute, 15 November 2010 C´edric Villani University of Lyon & Institut Henri Poincar´e(Paris) Cutting-edge physics at the end of nineteenth century Long-time behavior of a (dilute) classical gas Take many (say 1020) small hard balls, bouncing against each other, in a box Let the gas evolve according to Newton’s equations Prediction by Maxwell and Boltzmann The distribution function is asymptotically Gaussian v 2 f(t, x, v) a exp | | as t ≃ − 2T → ∞ Based on four major conceptual advances 1865-1875 Major modelling advance: Boltzmann equation • Major mathematical advance: the statistical entropy • Major physical advance: macroscopic irreversibility • Major PDE advance: qualitative functional study • Let us review these advances = journey around centennial scientific problems ⇒ The Boltzmann equation Models rarefied gases (Maxwell 1865, Boltzmann 1872) f(t, x, v) : density of particles in (x, v) space at time t f(t, x, v) dxdv = fraction of mass in dxdv The Boltzmann equation (without boundaries) Unknown = time-dependent distribution f(t, x, v): ∂f 3 ∂f + v = Q(f,f) = ∂t i ∂x Xi=1 i ′ ′ B(v v∗,σ) f(t, x, v )f(t, x, v∗) f(t, x, v)f(t, x, v∗) dv∗ dσ R3 2 − − Z v∗ ZS h i The Boltzmann equation (without boundaries) Unknown = time-dependent distribution f(t, x, v): ∂f 3 ∂f + v = Q(f,f) = ∂t i ∂x Xi=1 i ′ ′ B(v v∗,σ) f(t, x, v )f(t, x, v∗) f(t, x, v)f(t, x, v∗) dv∗ dσ R3 2 − − Z v∗ ZS h i The Boltzmann equation (without boundaries) Unknown = time-dependent distribution -
A Molecular Modeler's Guide to Statistical Mechanics
A Molecular Modeler’s Guide to Statistical Mechanics Course notes for BIOE575 Daniel A. Beard Department of Bioengineering University of Washington Box 3552255 [email protected] (206) 685 9891 April 11, 2001 Contents 1 Basic Principles and the Microcanonical Ensemble 2 1.1 Classical Laws of Motion . 2 1.2 Ensembles and Thermodynamics . 3 1.2.1 An Ensembles of Particles . 3 1.2.2 Microscopic Thermodynamics . 4 1.2.3 Formalism for Classical Systems . 7 1.3 Example Problem: Classical Ideal Gas . 8 1.4 Example Problem: Quantum Ideal Gas . 10 2 Canonical Ensemble and Equipartition 15 2.1 The Canonical Distribution . 15 2.1.1 A Derivation . 15 2.1.2 Another Derivation . 16 2.1.3 One More Derivation . 17 2.2 More Thermodynamics . 19 2.3 Formalism for Classical Systems . 20 2.4 Equipartition . 20 2.5 Example Problem: Harmonic Oscillators and Blackbody Radiation . 21 2.5.1 Classical Oscillator . 22 2.5.2 Quantum Oscillator . 22 2.5.3 Blackbody Radiation . 23 2.6 Example Application: Poisson-Boltzmann Theory . 24 2.7 Brief Introduction to the Grand Canonical Ensemble . 25 3 Brownian Motion, Fokker-Planck Equations, and the Fluctuation-Dissipation Theo- rem 27 3.1 One-Dimensional Langevin Equation and Fluctuation- Dissipation Theorem . 27 3.2 Fokker-Planck Equation . 29 3.3 Brownian Motion of Several Particles . 30 3.4 Fluctuation-Dissipation and Brownian Dynamics . 32 1 Chapter 1 Basic Principles and the Microcanonical Ensemble The first part of this course will consist of an introduction to the basic principles of statistical mechanics (or statistical physics) which is the set of theoretical techniques used to understand microscopic systems and how microscopic behavior is reflected on the macroscopic scale. -
Entropy: from the Boltzmann Equation to the Maxwell Boltzmann Distribution
Entropy: From the Boltzmann equation to the Maxwell Boltzmann distribution A formula to relate entropy to probability Often it is a lot more useful to think about entropy in terms of the probability with which different states are occupied. Lets see if we can describe entropy as a function of the probability distribution between different states. N! WN particles = n1!n2!....nt! stirling (N e)N N N W = = N particles n1 n2 nt n1 n2 nt (n1 e) (n2 e) ....(nt e) n1 n2 ...nt with N pi = ni 1 W = N particles n1 n2 nt p1 p2 ...pt takeln t lnWN particles = "#ni ln pi i=1 divide N particles t lnW1particle = "# pi ln pi i=1 times k t k lnW1particle = "k# pi ln pi = S1particle i=1 and t t S = "N k p ln p = "R p ln p NA A # i # i i i=1 i=1 ! Think about how this equation behaves for a moment. If any one of the states has a probability of occurring equal to 1, then the ln pi of that state is 0 and the probability of all the other states has to be 0 (the sum over all probabilities has to be 1). So the entropy of such a system is 0. This is exactly what we would have expected. In our coin flipping case there was only one way to be all heads and the W of that configuration was 1. Also, and this is not so obvious, the maximal entropy will result if all states are equally populated (if you want to see a mathematical proof of this check out Ken Dill’s book on page 85). -
Boltzmann Equation II: Binary Collisions
Physics 127b: Statistical Mechanics Boltzmann Equation II: Binary Collisions Binary collisions in a classical gas Scattering out Scattering in v'1 v'2 v 1 v 2 R v 2 v 1 v'2 v'1 Center of V' Mass Frame V θ θ b sc sc R V V' Figure 1: Binary collisions in a gas: top—lab frame; bottom—centre of mass frame Binary collisions in a gas are very similar, except that the scattering is off another molecule. An individual scattering process is, of course, simplest to describe in the center of mass frame in terms of the relative E velocity V =Ev1 −Ev2. However the center of mass frame is different for different collisions, so we must keep track of the results in the lab frame, and this makes the calculation rather intricate. I will indicate the main ideas here, and refer you to Reif or Landau and Lifshitz for precise discussions. Lets first set things up in the lab frame. Again we consider the pair of scattering in and scattering out processes that are space-time inverses, and so have identical cross sections. We can write abstractly for the scattering out from velocity vE1 due to collisions with molecules with all velocities vE2, which will clearly be proportional to the number f (vE1) of molecules at vE1 (which we write as f1—sorry, not the same notation as in the previous sections where f1 denoted the deviation of f from the equilibrium distribution!) and the 3 3 number f2d v2 ≡ f(vE2)d v2 in each velocity volume element, and then we must integrate over all possible vE0 vE0 outgoing velocities 1 and 2 ZZZ df (vE ) 1 =− w(vE0 , vE0 ;Ev , vE )f f d3v d3v0 d3v0 . -
Lecture 6: Entropy
Matthew Schwartz Statistical Mechanics, Spring 2019 Lecture 6: Entropy 1 Introduction In this lecture, we discuss many ways to think about entropy. The most important and most famous property of entropy is that it never decreases Stot > 0 (1) Here, Stot means the change in entropy of a system plus the change in entropy of the surroundings. This is the second law of thermodynamics that we met in the previous lecture. There's a great quote from Sir Arthur Eddington from 1927 summarizing the importance of the second law: If someone points out to you that your pet theory of the universe is in disagreement with Maxwell's equationsthen so much the worse for Maxwell's equations. If it is found to be contradicted by observationwell these experimentalists do bungle things sometimes. But if your theory is found to be against the second law of ther- modynamics I can give you no hope; there is nothing for it but to collapse in deepest humiliation. Another possibly relevant quote, from the introduction to the statistical mechanics book by David Goodstein: Ludwig Boltzmann who spent much of his life studying statistical mechanics, died in 1906, by his own hand. Paul Ehrenfest, carrying on the work, died similarly in 1933. Now it is our turn to study statistical mechanics. There are many ways to dene entropy. All of them are equivalent, although it can be hard to see. In this lecture we will compare and contrast dierent denitions, building up intuition for how to think about entropy in dierent contexts. The original denition of entropy, due to Clausius, was thermodynamic. -
Boltzmann Equation
Boltzmann Equation ● Velocity distribution functions of particles ● Derivation of Boltzmann Equation Ludwig Eduard Boltzmann (February 20, 1844 - September 5, 1906), an Austrian physicist famous for the invention of statistical mechanics. Born in Vienna, Austria-Hungary, he committed suicide in 1906 by hanging himself while on holiday in Duino near Trieste in Italy. Distribution Function (probability density function) Random variable y is distributed with the probability density function f(y) if for any interval [a b] the probability of a<y<b is equal to b P=∫ f ydy a f(y) is always non-negative ∫ f ydy=1 Velocity space Axes u,v,w in velocity space v dv have the same directions as dv axes x,y,z in physical du dw u space. Each molecule can be v represented in velocity space by the point defined by its velocity vector v with components (u,v,w) w Velocity distribution function Consider a sample of gas that is homogeneous in physical space and contains N identical molecules. Velocity distribution function is defined by d N =Nf vd ud v d w (1) where dN is the number of molecules in the sample with velocity components (ui,vi,wi) such that u<ui<u+du, v<vi<v+dv, w<wi<w+dw dv = dudvdw is a volume element in the velocity space. Consequently, dN is the number of molecules in velocity space element dv. Functional statement if often omitted, so f(v) is designated as f Phase space distribution function Macroscopic properties of the flow are functions of position and time, so the distribution function depends on position and time as well as velocity. -
Dirty Tricks for Statistical Mechanics
Dirty tricks for statistical mechanics Martin Grant Physics Department, McGill University c MG, August 2004, version 0.91 ° ii Preface These are lecture notes for PHYS 559, Advanced Statistical Mechanics, which I’ve taught at McGill for many years. I’m intending to tidy this up into a book, or rather the first half of a book. This half is on equilibrium, the second half would be on dynamics. These were handwritten notes which were heroically typed by Ryan Porter over the summer of 2004, and may someday be properly proof-read by me. Even better, maybe someday I will revise the reasoning in some of the sections. Some of it can be argued better, but it was too much trouble to rewrite the handwritten notes. I am also trying to come up with a good book title, amongst other things. The two titles I am thinking of are “Dirty tricks for statistical mechanics”, and “Valhalla, we are coming!”. Clearly, more thinking is necessary, and suggestions are welcome. While these lecture notes have gotten longer and longer until they are al- most self-sufficient, it is always nice to have real books to look over. My favorite modern text is “Lectures on Phase Transitions and the Renormalisation Group”, by Nigel Goldenfeld (Addison-Wesley, Reading Mass., 1992). This is referred to several times in the notes. Other nice texts are “Statistical Physics”, by L. D. Landau and E. M. Lifshitz (Addison-Wesley, Reading Mass., 1970) par- ticularly Chaps. 1, 12, and 14; “Statistical Mechanics”, by S.-K. Ma (World Science, Phila., 1986) particularly Chaps. -
Generalized Molecular Chaos Hypothesis and the H-Theorem: Problem of Constraints and Amendment of Nonextensive Statistical Mechanics
Generalized molecular chaos hypothesis and the H-theorem: Problem of constraints and amendment of nonextensive statistical mechanics Sumiyoshi Abe1,2,3 1Department of Physical Engineering, Mie University, Mie 514-8507, Japan*) 2Institut Supérieur des Matériaux et Mécaniques Avancés, 44 F. A. Bartholdi, 72000 Le Mans, France 3Inspire Institute Inc., McLean, Virginia 22101, USA Abstract Quite unexpectedly, kinetic theory is found to specify the correct definition of average value to be employed in nonextensive statistical mechanics. It is shown that the normal average is consistent with the generalized Stosszahlansatz (i.e., molecular chaos hypothesis) and the associated H-theorem, whereas the q-average widely used in the relevant literature is not. In the course of the analysis, the distributions with finite cut-off factors are rigorously treated. Accordingly, the formulation of nonextensive statistical mechanics is amended based on the normal average. In addition, the Shore- Johnson theorem, which supports the use of the q-average, is carefully reexamined, and it is found that one of the axioms may not be appropriate for systems to be treated within the framework of nonextensive statistical mechanics. PACS number(s): 05.20.Dd, 05.20.Gg, 05.90.+m ____________________________ *) Permanent address 1 I. INTRODUCTION There exist a number of physical systems that possess exotic properties in view of traditional Boltzmann-Gibbs statistical mechanics. They are said to be statistical- mechanically anomalous, since they often exhibit and realize broken ergodicity, strong correlation between elements, (multi)fractality of phase-space/configuration-space portraits, and long-range interactions, for example. In the past decade, nonextensive statistical mechanics [1,2], which is a generalization of the Boltzmann-Gibbs theory, has been drawing continuous attention as a possible theoretical framework for describing these systems. -
Nonlinear Electrostatics. the Poisson-Boltzmann Equation
Nonlinear Electrostatics. The Poisson-Boltzmann Equation C. G. Gray* and P. J. Stiles# *Department of Physics, University of Guelph, Guelph, ON N1G2W1, Canada ([email protected]) #Department of Molecular Sciences, Macquarie University, NSW 2109, Australia ([email protected]) The description of a conducting medium in thermal equilibrium, such as an electrolyte solution or a plasma, involves nonlinear electrostatics, a subject rarely discussed in the standard electricity and magnetism textbooks. We consider in detail the case of the electrostatic double layer formed by an electrolyte solution near a uniformly charged wall, and we use mean-field or Poisson-Boltzmann (PB) theory to calculate the mean electrostatic potential and the mean ion concentrations, as functions of distance from the wall. PB theory is developed from the Gibbs variational principle for thermal equilibrium of minimizing the system free energy. We clarify the key issue of which free energy (Helmholtz, Gibbs, grand, …) should be used in the Gibbs principle; this turns out to depend not only on the specified conditions in the bulk electrolyte solution (e.g., fixed volume or fixed pressure), but also on the specified surface conditions, such as fixed surface charge or fixed surface potential. Despite its nonlinearity the PB equation for the mean electrostatic potential can be solved analytically for planar or wall geometry, and we present analytic solutions for both a full electrolyte, and for an ionic solution which contains only counterions, i.e. ions of sign opposite to that of the wall charge. This latter case has some novel features. We also use the free energy to discuss the inter-wall forces which arise when the two parallel charged walls are sufficiently close to permit their double layers to overlap.