Statistical mechanics

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In physics, statistical mechanics is a mathematical framework that applies statistical methods and probability theory to large assemblies of microscopic entities. It does not assume or postulate any natural laws, but explains the macroscopic behavior of nature from the behavior of such ensembles.

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Statistical mechanics arose out of the development of classical thermodynamics, a field for which it was successful in explaining macroscopic physical properties—such as temperature, pressure, and heat capacity—in terms of microscopic parameters that fluctuate about average values and are characterized by probability distributions. This established the fields of statistical thermodynamics and statistical physics.

The founding of the field of statistical mechanics is generally credited to three physicists:

While classical thermodynamics is primarily concerned with thermodynamic equilibrium, statistical mechanics has been applied in non-equilibrium statistical mechanics to the issues of microscopically modeling the speed of irreversible processes that are driven by imbalances. Examples of such processes include chemical reactions and flows of particles and heat. The fluctuation–dissipation theorem is the basic knowledge obtained from applying non-equilibrium statistical mechanics to study the simplest non-equilibrium situation of a steady state current flow in a system of many particles.

Principles: mechanics and ensembles

In physics, two types of mechanics are usually examined: classical mechanics and quantum mechanics. For both types of mechanics, the standard mathematical approach is to consider two concepts:

Using these two concepts, the state at any other time, past or future, can in principle be calculated. There is however a disconnect between these laws and everyday life experiences, as we do not find it necessary (nor even theoretically possible) to know exactly at a microscopic level the simultaneous positions and velocities of each molecule while carrying out processes at the human scale (for example, when performing a chemical reaction). Statistical mechanics fills this disconnection between the laws of mechanics and the practical experience of incomplete knowledge, by adding some uncertainty about which state the system is in.

Whereas ordinary mechanics only considers the behaviour of a single state, statistical mechanics introduces the statistical ensemble, which is a large collection of virtual, independent copies of the system in various states. The statistical ensemble is a probability distribution over all possible states of the system. In classical statistical mechanics, the ensemble is a probability distribution over phase points (as opposed to a single phase point in ordinary mechanics), usually represented as a distribution in a phase space with canonical coordinate axes. In quantum statistical mechanics, the ensemble is a probability distribution over pure states, [note 1] and can be compactly summarized as a density matrix.

As is usual for probabilities, the ensemble can be interpreted in different ways: [1]

These two meanings are equivalent for many purposes, and will be used interchangeably in this article.

However the probability is interpreted, each state in the ensemble evolves over time according to the equation of motion. Thus, the ensemble itself (the probability distribution over states) also evolves, as the virtual systems in the ensemble continually leave one state and enter another. The ensemble evolution is given by the Liouville equation (classical mechanics) or the von Neumann equation (quantum mechanics). These equations are simply derived by the application of the mechanical equation of motion separately to each virtual system contained in the ensemble, with the probability of the virtual system being conserved over time as it evolves from state to state.

One special class of ensemble is those ensembles that do not evolve over time. These ensembles are known as equilibrium ensembles and their condition is known as statistical equilibrium. Statistical equilibrium occurs if, for each state in the ensemble, the ensemble also contains all of its future and past states with probabilities equal to the probability of being in that state. [note 2] The study of equilibrium ensembles of isolated systems is the focus of statistical thermodynamics. Non-equilibrium statistical mechanics addresses the more general case of ensembles that change over time, and/or ensembles of non-isolated systems.

Statistical thermodynamics

The primary goal of statistical thermodynamics (also known as equilibrium statistical mechanics) is to derive the classical thermodynamics of materials in terms of the properties of their constituent particles and the interactions between them. In other words, statistical thermodynamics provides a connection between the macroscopic properties of materials in thermodynamic equilibrium, and the microscopic behaviours and motions occurring inside the material.

Whereas statistical mechanics proper involves dynamics, here the attention is focussed on statistical equilibrium (steady state). Statistical equilibrium does not mean that the particles have stopped moving (mechanical equilibrium), rather, only that the ensemble is not evolving.

Fundamental postulate

A sufficient (but not necessary) condition for statistical equilibrium with an isolated system is that the probability distribution is a function only of conserved properties (total energy, total particle numbers, etc.). [1] There are many different equilibrium ensembles that can be considered, and only some of them correspond to thermodynamics. [1] Additional postulates are necessary to motivate why the ensemble for a given system should have one form or another.

A common approach found in many textbooks is to take the equal a priori probability postulate. [2] This postulate states that

For an isolated system with an exactly known energy and exactly known composition, the system can be found with equal probability in any microstate consistent with that knowledge.

The equal a priori probability postulate therefore provides a motivation for the microcanonical ensemble described below. There are various arguments in favour of the equal a priori probability postulate:

Other fundamental postulates for statistical mechanics have also been proposed. [4] [5] [6] For example, recent studies shows that the theory of statistical mechanics can be built without the equal a priori probability postulate. [5] [6] One such formalism is based on the fundamental thermodynamic relation together with the following set of postulates: [5]

  1. The probability density function is proportional to some function of the ensemble parameters and random variables.
  2. Thermodynamic state functions are described by ensemble averages of random variables.
  3. The entropy as defined by Gibbs entropy formula matches with the entropy as defined in classical thermodynamics.

where the third postulate can be replaced by the following: [6]

  1. At infinite temperature, all the microstates have the same probability.

Three thermodynamic ensembles

There are three equilibrium ensembles with a simple form that can be defined for any isolated system bounded inside a finite volume. [1] These are the most often discussed ensembles in statistical thermodynamics. In the macroscopic limit (defined below) they all correspond to classical thermodynamics.

Microcanonical ensemble
describes a system with a precisely given energy and fixed composition (precise number of particles). The microcanonical ensemble contains with equal probability each possible state that is consistent with that energy and composition.
Canonical ensemble
describes a system of fixed composition that is in thermal equilibrium [note 3] with a heat bath of a precise temperature. The canonical ensemble contains states of varying energy but identical composition; the different states in the ensemble are accorded different probabilities depending on their total energy.
Grand canonical ensemble
describes a system with non-fixed composition (uncertain particle numbers) that is in thermal and chemical equilibrium with a thermodynamic reservoir. The reservoir has a precise temperature, and precise chemical potentials for various types of particle. The grand canonical ensemble contains states of varying energy and varying numbers of particles; the different states in the ensemble are accorded different probabilities depending on their total energy and total particle numbers.

For systems containing many particles (the thermodynamic limit), all three of the ensembles listed above tend to give identical behaviour. It is then simply a matter of mathematical convenience which ensemble is used. [7] The Gibbs theorem about equivalence of ensembles [8] was developed into the theory of concentration of measure phenomenon, [9] which has applications in many areas of science, from functional analysis to methods of artificial intelligence and big data technology. [10]

Important cases where the thermodynamic ensembles do not give identical results include:

In these cases the correct thermodynamic ensemble must be chosen as there are observable differences between these ensembles not just in the size of fluctuations, but also in average quantities such as the distribution of particles. The correct ensemble is that which corresponds to the way the system has been prepared and characterized—in other words, the ensemble that reflects the knowledge about that system. [2]

Thermodynamic ensembles [1]
Microcanonical Canonical Grand canonical
Fixed variables
Microscopic features
Macroscopic function

Calculation methods

Once the characteristic state function for an ensemble has been calculated for a given system, that system is 'solved' (macroscopic observables can be extracted from the characteristic state function). Calculating the characteristic state function of a thermodynamic ensemble is not necessarily a simple task, however, since it involves considering every possible state of the system. While some hypothetical systems have been exactly solved, the most general (and realistic) case is too complex for an exact solution. Various approaches exist to approximate the true ensemble and allow calculation of average quantities.

Exact

There are some cases which allow exact solutions.

  • For very small microscopic systems, the ensembles can be directly computed by simply enumerating over all possible states of the system (using exact diagonalization in quantum mechanics, or integral over all phase space in classical mechanics).
  • Some large systems consist of many separable microscopic systems, and each of the subsystems can be analysed independently. Notably, idealized gases of non-interacting particles have this property, allowing exact derivations of Maxwell–Boltzmann statistics, Fermi–Dirac statistics, and Bose–Einstein statistics. [2]
  • A few large systems with interaction have been solved. By the use of subtle mathematical techniques, exact solutions have been found for a few toy models. [11] Some examples include the Bethe ansatz, square-lattice Ising model in zero field, hard hexagon model.

Monte Carlo

One approximate approach that is particularly well suited to computers is the Monte Carlo method, which examines just a few of the possible states of the system, with the states chosen randomly (with a fair weight). As long as these states form a representative sample of the whole set of states of the system, the approximate characteristic function is obtained. As more and more random samples are included, the errors are reduced to an arbitrarily low level.

Other

  • For rarefied non-ideal gases, approaches such as the cluster expansion use perturbation theory to include the effect of weak interactions, leading to a virial expansion. [12]
  • For dense fluids, another approximate approach is based on reduced distribution functions, in particular the radial distribution function. [12]
  • Molecular dynamics computer simulations can be used to calculate microcanonical ensemble averages, in ergodic systems. With the inclusion of a connection to a stochastic heat bath, they can also model canonical and grand canonical conditions.
  • Mixed methods involving non-equilibrium statistical mechanical results (see below) may be useful.

Non-equilibrium statistical mechanics

Many physical phenomena involve quasi-thermodynamic processes out of equilibrium, for example:

All of these processes occur over time with characteristic rates. These rates are important in engineering. The field of non-equilibrium statistical mechanics is concerned with understanding these non-equilibrium processes at the microscopic level. (Statistical thermodynamics can only be used to calculate the final result, after the external imbalances have been removed and the ensemble has settled back down to equilibrium.)

In principle, non-equilibrium statistical mechanics could be mathematically exact: ensembles for an isolated system evolve over time according to deterministic equations such as Liouville's equation or its quantum equivalent, the von Neumann equation. These equations are the result of applying the mechanical equations of motion independently to each state in the ensemble. Unfortunately, these ensemble evolution equations inherit much of the complexity of the underlying mechanical motion, and so exact solutions are very difficult to obtain. Moreover, the ensemble evolution equations are fully reversible and do not destroy information (the ensemble's Gibbs entropy is preserved). In order to make headway in modelling irreversible processes, it is necessary to consider additional factors besides probability and reversible mechanics.

Non-equilibrium mechanics is therefore an active area of theoretical research as the range of validity of these additional assumptions continues to be explored. A few approaches are described in the following subsections.

Stochastic methods

One approach to non-equilibrium statistical mechanics is to incorporate stochastic (random) behaviour into the system. Stochastic behaviour destroys information contained in the ensemble. While this is technically inaccurate (aside from hypothetical situations involving black holes, a system cannot in itself cause loss of information), the randomness is added to reflect that information of interest becomes converted over time into subtle correlations within the system, or to correlations between the system and environment. These correlations appear as chaotic or pseudorandom influences on the variables of interest. By replacing these correlations with randomness proper, the calculations can be made much easier.

  • Boltzmann transport equation : An early form of stochastic mechanics appeared even before the term "statistical mechanics" had been coined, in studies of kinetic theory. James Clerk Maxwell had demonstrated that molecular collisions would lead to apparently chaotic motion inside a gas. Ludwig Boltzmann subsequently showed that, by taking this molecular chaos for granted as a complete randomization, the motions of particles in a gas would follow a simple Boltzmann transport equation that would rapidly restore a gas to an equilibrium state (see H-theorem). The Boltzmann transport equation and related approaches are important tools in non-equilibrium statistical mechanics due to their extreme simplicity. These approximations work well in systems where the "interesting" information is immediately (after just one collision) scrambled up into subtle correlations, which essentially restricts them to rarefied gases. The Boltzmann transport equation has been found to be very useful in simulations of electron transport in lightly doped semiconductors (in transistors), where the electrons are indeed analogous to a rarefied gas. A quantum technique related in theme is the random phase approximation.
  • BBGKY hierarchy : In liquids and dense gases, it is not valid to immediately discard the correlations between particles after one collision. The BBGKY hierarchy (Bogoliubov–Born–Green–Kirkwood–Yvon hierarchy) gives a method for deriving Boltzmann-type equations but also extending them beyond the dilute gas case, to include correlations after a few collisions.
  • Keldysh formalism (a.k.a. NEGF—non-equilibrium Green functions): A quantum approach to including stochastic dynamics is found in the Keldysh formalism. This approach is often used in electronic quantum transport calculations.
  • Stochastic Liouville equation.

Near-equilibrium methods

Another important class of non-equilibrium statistical mechanical models deals with systems that are only very slightly perturbed from equilibrium. With very small perturbations, the response can be analysed in linear response theory. A remarkable result, as formalized by the fluctuation–dissipation theorem, is that the response of a system when near equilibrium is precisely related to the fluctuations that occur when the system is in total equilibrium. Essentially, a system that is slightly away from equilibrium—whether put there by external forces or by fluctuations—relaxes towards equilibrium in the same way, since the system cannot tell the difference or "know" how it came to be away from equilibrium. [12] :664

This provides an indirect avenue for obtaining numbers such as ohmic conductivity and thermal conductivity by extracting results from equilibrium statistical mechanics. Since equilibrium statistical mechanics is mathematically well defined and (in some cases) more amenable for calculations, the fluctuation–dissipation connection can be a convenient shortcut for calculations in near-equilibrium statistical mechanics.

A few of the theoretical tools used to make this connection include:

Hybrid methods

An advanced approach uses a combination of stochastic methods and linear response theory. As an example, one approach to compute quantum coherence effects (weak localization, conductance fluctuations) in the conductance of an electronic system is the use of the Green–Kubo relations, with the inclusion of stochastic dephasing by interactions between various electrons by use of the Keldysh method. [13] [14]

Applications outside thermodynamics

The ensemble formalism also can be used to analyze general mechanical systems with uncertainty in knowledge about the state of a system. Ensembles are also used in:

History

In 1738, Swiss physicist and mathematician Daniel Bernoulli published Hydrodynamica which laid the basis for the kinetic theory of gases. In this work, Bernoulli posited the argument, still used to this day, that gases consist of great numbers of molecules moving in all directions, that their impact on a surface causes the gas pressure that we feel, and that what we experience as heat is simply the kinetic energy of their motion. [4]

In 1859, after reading a paper on the diffusion of molecules by Rudolf Clausius, Scottish physicist James Clerk Maxwell formulated the Maxwell distribution of molecular velocities, which gave the proportion of molecules having a certain velocity in a specific range. [15] This was the first-ever statistical law in physics. [16] Maxwell also gave the first mechanical argument that molecular collisions entail an equalization of temperatures and hence a tendency towards equilibrium. [17] Five years later, in 1864, Ludwig Boltzmann, a young student in Vienna, came across Maxwell's paper and spent much of his life developing the subject further.

Statistical mechanics was initiated in the 1870s with the work of Boltzmann, much of which was collectively published in his 1896 Lectures on Gas Theory. [18] Boltzmann's original papers on the statistical interpretation of thermodynamics, the H-theorem, transport theory, thermal equilibrium, the equation of state of gases, and similar subjects, occupy about 2,000 pages in the proceedings of the Vienna Academy and other societies. Boltzmann introduced the concept of an equilibrium statistical ensemble and also investigated for the first time non-equilibrium statistical mechanics, with his H-theorem.

The term "statistical mechanics" was coined by the American mathematical physicist J. Willard Gibbs in 1884. [19] [note 4] "Probabilistic mechanics" might today seem a more appropriate term, but "statistical mechanics" is firmly entrenched. [20] Shortly before his death, Gibbs published in 1902 Elementary Principles in Statistical Mechanics , a book which formalized statistical mechanics as a fully general approach to address all mechanical systems—macroscopic or microscopic, gaseous or non-gaseous. [1] Gibbs' methods were initially derived in the framework classical mechanics, however they were of such generality that they were found to adapt easily to the later quantum mechanics, and still form the foundation of statistical mechanics to this day. [2]

See also

Notes

  1. The probabilities in quantum statistical mechanics should not be confused with quantum superposition. While a quantum ensemble can contain states with quantum superpositions, a single quantum state cannot be used to represent an ensemble.
  2. Statistical equilibrium should not be confused with mechanical equilibrium . The latter occurs when a mechanical system has completely ceased to evolve even on a microscopic scale, due to being in a state with a perfect balancing of forces. Statistical equilibrium generally involves states that are very far from mechanical equilibrium.
  3. The transitive thermal equilibrium (as in, "X is thermal equilibrium with Y") used here means that the ensemble for the first system is not perturbed when the system is allowed to weakly interact with the second system.
  4. According to Gibbs, the term "statistical", in the context of mechanics, i.e. statistical mechanics, was first used by the Scottish physicist James Clerk Maxwell in 1871. From: J. Clerk Maxwell, Theory of Heat (London, England: Longmans, Green, and Co., 1871), p. 309: "In dealing with masses of matter, while we do not perceive the individual molecules, we are compelled to adopt what I have described as the statistical method of calculation, and to abandon the strict dynamical method, in which we follow every motion by the calculus."

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<span class="mw-page-title-main">Entropy</span> Property of a thermodynamic system

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<span class="mw-page-title-main">Thermodynamics</span> Physics of heat, work, and temperature

Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of thermodynamics which convey a quantitative description using measurable macroscopic physical quantities, but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering, especially physical chemistry, biochemistry, chemical engineering and mechanical engineering, but also in other complex fields such as meteorology.

Timeline of thermodynamics

A timeline of events in the history of thermodynamics.

In physics, specifically statistical mechanics, an ensemble is an idealization consisting of a large number of virtual copies of a system, considered all at once, each of which represents a possible state that the real system might be in. In other words, a statistical ensemble is a set of systems of particles used in statistical mechanics to describe a single system. The concept of an ensemble was introduced by J. Willard Gibbs in 1902.

<span class="mw-page-title-main">Ideal gas</span> Mathematical model which approximates the behavior of real gases

An ideal gas is a theoretical gas composed of many randomly moving point particles that are not subject to interparticle interactions. The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state, and is amenable to analysis under statistical mechanics. The requirement of zero interaction can often be relaxed if, for example, the interaction is perfectly elastic or regarded as point-like collisions.

In classical statistical mechanics, the H-theorem, introduced by Ludwig Boltzmann in 1872, describes the tendency to decrease in the quantity H in a nearly-ideal gas of molecules. As this quantity H was meant to represent the entropy of thermodynamics, the H-theorem was an early demonstration of the power of statistical mechanics as it claimed to derive the second law of thermodynamics—a statement about fundamentally irreversible processes—from reversible microscopic mechanics. It is thought to prove the second law of thermodynamics, albeit under the assumption of low-entropy initial conditions.

<span class="mw-page-title-main">Ludwig Boltzmann</span> Austrian physicist and philosopher (1844–1906)

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In statistical mechanics, the grand canonical ensemble is the statistical ensemble that is used to represent the possible states of a mechanical system of particles that are in thermodynamic equilibrium with a reservoir. The system is said to be open in the sense that the system can exchange energy and particles with a reservoir, so that various possible states of the system can differ in both their total energy and total number of particles. The system's volume, shape, and other external coordinates are kept the same in all possible states of the system.

In statistical mechanics, the microcanonical ensemble is a statistical ensemble that represents the possible states of a mechanical system whose total energy is exactly specified. The system is assumed to be isolated in the sense that it cannot exchange energy or particles with its environment, so that the energy of the system does not change with time.

In statistical mechanics, a canonical ensemble is the statistical ensemble that represents the possible states of a mechanical system in thermal equilibrium with a heat bath at a fixed temperature. The system can exchange energy with the heat bath, so that the states of the system will differ in total energy.

History of thermodynamics

The history of thermodynamics is a fundamental strand in the history of physics, the history of chemistry, and the history of science in general. Owing to the relevance of thermodynamics in much of science and technology, its history is finely woven with the developments of classical mechanics, quantum mechanics, magnetism, and chemical kinetics, to more distant applied fields such as meteorology, information theory, and biology (physiology), and to technological developments such as the steam engine, internal combustion engine, cryogenics and electricity generation. The development of thermodynamics both drove and was driven by atomic theory. It also, albeit in a subtle manner, motivated new directions in probability and statistics; see, for example, the timeline of thermodynamics.

In physics, maximum entropy thermodynamics views equilibrium thermodynamics and statistical mechanics as inference processes. More specifically, MaxEnt applies inference techniques rooted in Shannon information theory, Bayesian probability, and the principle of maximum entropy. These techniques are relevant to any situation requiring prediction from incomplete or insufficient data. MaxEnt thermodynamics began with two papers by Edwin T. Jaynes published in the 1957 Physical Review.

Microstate (statistical mechanics) Specific microscopic configuration of a thermodynamic system

In statistical mechanics, a microstate is a specific microscopic configuration of a thermodynamic system that the system may occupy with a certain probability in the course of its thermal fluctuations. In contrast, the macrostate of a system refers to its macroscopic properties, such as its temperature, pressure, volume and density. Treatments on statistical mechanics define a macrostate as follows: a particular set of values of energy, the number of particles, and the volume of an isolated thermodynamic system is said to specify a particular macrostate of it. In this description, microstates appear as different possible ways the system can achieve a particular macrostate.

The mathematical expressions for thermodynamic entropy in the statistical thermodynamics formulation established by Ludwig Boltzmann and J. Willard Gibbs in the 1870s are similar to the information entropy by Claude Shannon and Ralph Hartley, developed in the 1940s.

The concept entropy was first developed by German physicist Rudolf Clausius in the mid-nineteenth century as a thermodynamic property that predicts that certain spontaneous processes are irreversible or impossible. In statistical mechanics, entropy is formulated as a statistical property using probability theory. The statistical entropy perspective was introduced in 1870 by Austrian physicist Ludwig Boltzmann, who established a new field of physics that provided the descriptive linkage between the macroscopic observation of nature and the microscopic view based on the rigorous treatment of a large ensembles of microstates that constitute thermodynamic systems.

Table of thermodynamic equations

This article is a summary of common equations and quantities in thermodynamics.

Boltzmanns entropy formula Equation in statistical mechanics

In statistical mechanics, Boltzmann's equation is a probability equation relating the entropy , also written as , of an ideal gas to the multiplicity, the number of real microstates corresponding to the gas's macrostate:

<span class="mw-page-title-main">Temperature</span> Physical quantity that expresses hot and cold

Temperature is a physical quantity that expresses the hotness of matter or radiation.

Stochastic thermodynamics is an emergent field of research in statistical mechanics that uses stochastic variables to better understand the non-equilibrium dynamics present in many microscopic systems such as colloidal particles, biopolymers, enzymes, and molecular motors.

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  15. See:
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