Detailed balance has a counterpart in non-equilibrium steady states

R. M. L. Evans

Published 2004-08-27, updated 2004-11-15Version 2

When modelling driven steady states of matter, it is common practice either to choose transition rates arbitrarily, or to assume that the principle of detailed balance remains valid away from equilibrium. Neither of those practices is theoretically well founded. Hypothesising ergodicity constrains the transition rates in driven steady states to respect relations analogous to, but different from the equilibrium principle of detailed balance. The constraints arise from demanding that the design of any model system contains no information extraneous to the microscopic laws of motion and the macroscopic observables. This prevents over-description of the non-equilibrium reservoir, and implies that not all stochastic equations of motion are equally valid. The resulting recipe for transition rates has many features in common with equilibrium statistical mechanics.