Statistical mechanics

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

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.

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

For an isolated system with an exactly known energy and exactly known composition, the system can be found with

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:

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.
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.

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

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.

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.

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.)

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.

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: