Statistical Mechanics

Statistical mechanics or statistical thermodynamics is a branch of physics that applies probability theory, which contains mathematical tools for dealing with large populations, to the study of the thermodynamic behavior of systems composed of a large number of particles. Statistical mechanics provides a framework for relating the microscopic properties of individual atoms and molecules to the macroscopic bulk properties of materials that can be observed in everyday life, thereby explaining thermodynamics as a result of the classical and quantum-mechanical descriptions of statistics and mechanics at the microscopic level.

Statistical mechanics provides a molecular-level interpretation of macroscopic thermodynamic quantities such as work, heat, free energy, and entropy. It enables the thermodynamic properties of bulk materials to be related to the spectroscopic data of individual molecules. This ability to make macroscopic predictions based on microscopic properties is the main advantage of statistical mechanics over classical thermodynamics. Both theories are governed by the second law of thermodynamics through the medium of entropy. However, entropy in thermodynamics can only be known empirically, whereas in statistical mechanics, it is a function of the distribution of the system on its micro-states.

Statistical mechanics was initiated in 1870 with the work of Austrian physicist Ludwig Boltzmann, much of which was collectively published in Boltzmann's 1896 Lectures on Gas Theory. 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. The term "statistical thermodynamics" was proposed for use by the American thermodynamicist and physical chemist J. Willard Gibbs in 1902. 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.