English

Alternative Derivation of the Partition Function for Generalized Ensembles

Statistical Mechanics 2013-09-10 v1

Abstract

A pedagogical approach for deriving the statistical mechanical partition function, in a manner that emphasizes the key role of entropy in connecting the microscopic states to thermodynamics, is introduced. The connections between the combinatoric formula S=klnWS= k \ln W applied to the Gibbs construction, the Gibbs entropy, S=kipilnpiS = -k \sum\limits_i p_i \ln p_i, and the microcanonical entropy expression S=klnΩS= k \ln \Omega are clarified. The condition for microcanonical equilibrium, and the associated role of the entropy in the thermodynamic potential is shown to arise naturally from the postulate of equal {\itshape a priori} states. The derivation of the canonical partition function follows simply by invoking the Gibbs ensemble construction at constant temperature and using the first and second law of thermodynamics (\emph{via} the fundamental equation dE=TdSPdV+μdNdE = TdS - PdV + \mu dN) that incorporate the conditions of conservation of energy and composition without the needs for explicit constraints; other ensemble follow easily. The central role of the entropy in establishing equilibrium for a given ensemble emerges naturally from the current approach. Connections to generalized ensemble theory also arise and are presented in this context.

Keywords

Cite

@article{arxiv.1309.2017,
  title  = {Alternative Derivation of the Partition Function for Generalized Ensembles},
  author = {Jonathan L. Belof and Brian Space},
  journal= {arXiv preprint arXiv:1309.2017},
  year   = {2013}
}
R2 v1 2026-06-22T01:23:03.052Z