Ontology of temperature in nonequilibrium systems

J Chem Phys. 2007 Jun 28;126(24):244506. doi: 10.1063/1.2743032.

Abstract

The laws of thermodynamics provide a clear concept of the temperature for an equilibrium system in the continuum limit. Meanwhile, the equipartition theorem allows one to make a connection between the ensemble average of the kinetic energy and the uniform temperature. When a system or its environment is far from equilibrium, however, such an association does not necessarily apply. In small systems, the regression hypothesis may not even apply. Herein, it is shown that in small nonequilibrium systems, the regression hypothesis still holds, though with a generalized definition of the temperature. The latter must now be defined for each such manifestation.