Statistical mechanics
In physics, statistical mechanics is a mathematical framework that applies statistical methods and probability theory to large assemblies of microscopic entities. Sometimes called statistical physics or statistical thermodynamics, its applications include many problems in the fields of physics, biology,[1] chemistry, neuroscience,[2] computer science,[3][4] information theory[5] and sociology.[6] Its main purpose is to clarify the properties of matter in aggregate, in terms of physical laws governing atomic motion.[7][8]
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.
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.
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.[9]
The founding of the field of statistical mechanics is generally credited to three physicists:
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.[10] This was the first-ever statistical law in physics.[11] Maxwell also gave the first mechanical argument that molecular collisions entail an equalization of temperatures and hence a tendency towards equilibrium.[12] 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.[13] 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.[14] 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:
"Probabilistic mechanics" might today seem a more appropriate term, but "statistical mechanics" is firmly entrenched.[16] 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.[17] 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.[18]
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 and can be compactly summarized as a density matrix.
As is usual for probabilities, the ensemble can be interpreted in different ways:[17]
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. (By contrast, mechanical equilibrium is a state with a balance of forces that has ceased to evolve.) 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.