Detailed Balance - History

History

The principle of detailed balance was explicitly introduced for collisions by Ludwig Boltzmann. In 1872, he proved his H-theorem using this principle. The arguments in favor of this property are founded upon microscopic reversibility. Albert Einstein in 1916 used this principle in a background for his quantum theory of emission and absorption of radiation.

In 1901, Rudolf Wegscheider introduced the principle of detailed balance for chemical kinetics. In particular, he demonstrated that the irreversible cycles are impossible and found explicitly the relations between kinetic constants that follow from the principle of detailed balance. In 1931, Lars Onsager used these relations in his works, for which he was awarded the 1968 Nobel Prize in Chemistry.

The principle of detailed balance is used in the Markov chain Monte Carlo methods since their invention in 1953. In particular, in the Metropolis–Hastings algorithm and in its important particular case, Gibbs sampling, it is used as a simple and reliable condition to provide the desirable equilibrium state.

Now, the principle of detailed balance is a standard part of the university courses in statistical mechanics, physical chemistry, chemical and physical kinetics.