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Foundations of Physics

Axioms for the Boltzmann Distribution

Adam M. Brandenburger, Kai Steverson

Published May 1, 2019• 5 citations
Publisher

Abstract

A fundamental postulate of statistical mechanics is that all microstates in an isolated system are equally probable. This postulate, which goes back to Boltzmann, has often been criticized for not having a clear physical foundation. In this note, we provide a derivation of the canonical (Boltzmann) distribution that avoids this postulate. In its place, we impose two axioms with physical interpretations. The first axiom (thermal equilibrium) ensures that, as our system of interest comes into contact with different heat baths, the ranking of states of the system by probability is unchanged. Physically, this axiom is a statement that in thermal equilibrium, population inversions do not arise. The second axiom (energy exchange) requires that, for any heat bath and any probability distribution on states, there is a universe consisting of a system and heat bath that can achieve this distribution. Physically, this axiom is a statement that energy flows between system and heat bath are unrestricted. We show that our two axioms identify the Boltzmann distribution.

DOI
10.1007/s10701-019-00257-z

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A fundamental postulate of statistical mechanics is that all microstates in an isolated system are equally probable. This postulate, which goes back to Boltzmann, has often been criticized for not having a clear physical foundation. In this note, we provide a derivation of the canonical (Boltzmann) distribution that avoids this postulate. In its place, we impose two axioms with physical interpretations. The first axiom (thermal equilibrium) ensures that, as our system of interest comes into contact with different heat baths, the ranking of states of the system by probability is unchanged. Physically, this axiom is a statement that in thermal equilibrium, population inversions do not arise. The second axiom (energy exchange) requires that, for any heat bath and any probability distribution on states, there is a universe consisting of a system and heat bath that can achieve this distribution. Physically, this axiom is a statement that energy flows between system and heat bath are unrestricted. We show that our two axioms identify the Boltzmann distribution.
A system, or a set of systems, is said to be in thermal equilibrium when no net flow of heat energy occurs between its constituent parts when they are connected by a path permeable to heat (a diathermal wall).1 This condition is the endpoint of a spontaneous process: if two bodies at different temperatures are brought into thermal contact, energy will flow from the higher-temperature object to the lower-temperature object until this flow ceases and the equilibrium state is achieved.3 Within a single system, thermal equilibrium is characterized by a temperature that is both spatially uniform (the same at all points) and temporally constant (unchanging over time).4 This uniformity of macroscopic properties—such as temperature and pressure—is what defines the state of the system.1 It is important to distinguish this from the broader state of thermodynamic equilibrium. Thermal equilibrium (uniform temperature) is a necessary component, but full thermodynamic equilibrium also requires mechanical equilibrium (uniform pressure) and diffusive equilibrium (uniform chemical potential).6 Systems can achieve thermal equilibrium without achieving full thermodynamic equilibrium.6 The Zeroth Law of Thermodynamics: The "Discovery" of Temperature The concept of temperature, while intuitive, requires a formal physical principle to exist as a measurable, fundamental property. This principle is the Zeroth Law of Thermodynamics. Although it was formulated and named after the First and Second Laws, its foundational role was recognized as a logical prerequisite for the entire structure of thermodynamics.8 The law states: If system A is in thermal equilibrium with system C, and system B is in thermal equilibrium with system C, then systems A and B are in thermal equilibrium with each other.1 In this construction, system C plays the role of a thermometer.13 The profound implication of this law is mathematical: it establishes thermal equilibrium as a transitive relation 9, or more formally, an equivalence relation.14 In mathematics, any equivalence relation partitioning a set of objects implies the existence of a common, scalar property shared by all members of a given equivalence class. The Zeroth Law thus proves the existence of a scalar function of state—a property we call temperature—that is common to all systems in mutual thermal equilibrium.9 The law is, therefore, the fundamental basis for defining temperature and building consistent, reproducible temperature scales.1 This axiomatic foundation also provides the logical origin for one of temperature's most critical characteristics: it is an intensive property. An intensive property is one that does not depend on the size or amount of the system.15 If a large system 'A' is in internal thermal equilibrium 6, any two parts of it, subsystems 'A1' and 'A2', must also be in thermal equilibrium with each other. By the Zeroth Law, a thermometer 'C' that is in thermal equilibrium with the whole system 'A' must also be in thermal equilibrium with 'A1' and 'A2' individually.13 The thermometer, therefore, gives the same reading for all three. This demonstrates that the temperature of a system in thermal equilibrium is the same as the temperature of any part of it.16
Using the concept of quantum wave probability, combined with the identity principle, we can derive the Boltzmann distribution, Fermi distribution, and Bose distribution. Different distributions correspond to different conditions. The Boltzmann condition corresponds to the Boltzmann distribution. The Fermi condition corresponds to the Fermi distribution. The Bose condition corresponds to the Bose distribution. This demonstrates that the foundation of these three statistical distributions is quantum wave probability, all originating from quantum mechanics. The Boltzmann distribution is also an independent quantum distribution and is not simply a sparse limit of the Fermi or Bose distributions. The essence of the Boltzmann distribution is a uniform distribution. The Fermi and Bose distributions are deviations from the uniform distribution. Boltzmann entropy based on the quantum wave probability can resolve the Gibbs paradox. Using this new approach, we can also derive the results of eigenstate thermalization. The equilibrium state is the state in which all eigenstates have the same temperatures. We need to rethink the fundamentals of statistical mechanics.
Introduction A cup of tea, left to its own, cools down while the surrounding air heats up until both have reached the same temperature, and a gas, confined to the left half of a room, uniformly spreads over the entire available space as soon as the confining wall is removed. Thermodynamics (TD) characterizes such processes in terms of an increase of thermodynamic entropy, which attains its maximum value at equilibrium, and the second law of thermodynamics posits that in an isolated system entropy cannot decrease. The aim of statistical mechanics (SM) is to explain the behaviour of these systems, in particular their conformity with the second law, in terms of the dynamical laws governing the individual molecules of which the systems are made up. In what follows these laws are assumed to be the ones of classical mechanics. An influential suggestion of how this could be achieved was made by Ludwig Boltzmann (1877), and variants of it are currently regarded by many as the most promising option among the plethora of approaches to SM. Although these variants share a commitment to Boltzmann's basic ideas, they differ widely in how these ideas are implemented and used. These differences become most tangible when we look at how the different approaches deal with probabilities. There are two fundamentally different ways of introducing probabilities into SM, and even within these two groups there are important disparities as regards both technical and interpretational issues.
Using the concept of quantum wave probability, combined with the identity principle, we can derive the Boltzmann distribution, Fermi distribution, and Bose distribution. Different distributions correspond to different conditions. The Boltzmann condition corresponds to the Boltzmann distribution. The Fermi condition corresponds to the Fermi distribution. The Bose condition corresponds to the Bose distribution. This demonstrates that the foundation of these three statistical distributions is quantum wave probability, all originating from quantum mechanics. The Boltzmann distribution is also an independent quantum distribution and is not simply a sparse limit of the Fermi or Bose distributions. The essence of the Boltzmann distribution is a uniform distribution. The Fermi and Bose distributions are deviations from the uniform distribution. Boltzmann entropy based on the quantum wave probability can resolve the Gibbs paradox. Using this new approach, we can also derive the results of eigenstate thermalization. The equilibrium state is the state in which all eigenstates have the same temperature. We need to rethink the fundamentals of statistical mechanics.
Two approaches to describing the thermodynamics of a subsystem that interacts with a thermal bath are considered. Within the first approach, the mean system energy E_{S} is identified with the expectation value of the system Hamiltonian, which is evaluated with respect to the overall (system+bath) equilibrium distribution. Within the second approach, the system partition function Z_{S} is considered as the fundamental quantity, which is postulated to be the ratio of the overall (system+bath) and the bath partition functions, and the standard thermodynamic relation E_{S}=-d(ln Z_{S})/dbeta is used to obtain the mean system energy. Employing both classical and quantum-mechanical treatments, the advantages and shortcomings of the two approaches are analyzed in detail for various different systems. It is shown that already within classical mechanics both approaches predict significantly different results for thermodynamic quantities provided the system-bath interaction is not bilinear or the system of interest consists of more than a single particle. Based on the results, it is concluded that the first approach is superior.