The branch of physics in which statistical methods are applied to the microscopic constituents of a system in order to predict its macroscopic properties. The earliest application of this method was Boltzmann's attempt to explain the thermodynamic properties of gases on the basis of the statistical properties of large assemblies of molecules.
In classical statistical mechanics, each particle is regarded as occupying a point in phase space, i.e. to have an exact position and momentum at any particular instant. The probability that this point will occupy any small volume of the phase space is taken to be proportional to the volume. The Maxwell-Boltzmann law gives the most probable distribution of the particles in phase space.
With the advent of quantum theory, the exactness of these premises was disturbed (by the Heisenberg uncertainty principle). In the quantum statistics that evolved as a result, the phase space is divided into cells, each having a volume hf, where h is the Planck constant and f is the number of degrees of freedom of the particles. This new concept led to Bose-Einstein statistics, and for particles obeying the Pauli exclusion principle, to Fermi-Dirac statistics.
Subjects: Chemistry — Physics.