Ensemble Equivalence for Distinguishable Particles

Abstract

Statistics of distinguishable particles has become relevant in systems of colloidal particles and in the context of applications of statistical mechanics to complex networks. In this paper, we present evidence that a commonly used expression for the partition function of a system of distinguishable particles leads to huge fluctuations of the number of particles in the grand canonical ensemble and, consequently, to nonequivalence of statistical ensembles. We will show that the alternative definition of the partition function including, naturally, Boltzmann’s correct counting factor for distinguishable particles solves the problem and restores ensemble equivalence. Finally, we also show that this choice for the partition function does not produce any inconsistency for a system of distinguishable localized particles, where the monoparticular partition function is not extensive.