Beyond Boltzmann-Gibbs statistics: maximum entropy hyperensembles out of equilibrium.
What is the best description that we can construct of a thermodynamic system that is not in equilibrium, given only one, or a few, extra parameters over and above those needed for a description of the same system at equilibrium? Here, we argue the most appropriate additional parameter is the nonequilibrium entropy of the system. Moreover, we should not attempt to estimate the probability distribution of the system directly, but rather the metaprobability (or hyperensemble) that the system is described by a particular probability distribution. The result is an entropic distribution with two parameters, one a nonequilibrium temperature, and the other a measure of distance from equilibrium. This dispersion parameter smoothly interpolates between certainty of a canonical distribution at equilibrium and great uncertainty as to the probability distribution as we move away from equilibrium. We deduce that, in general, large, rare fluctuations become far more common as we move away from equilibrium.
Crooks
Gavin E
GE
Physical Bioscience Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. gecrooks@lbl.gov