English

Maximum Entropy Principle, Equal Probability a Priori and Gibbs Paradox

Statistical Mechanics 2011-06-01 v2

Abstract

We prove that information-theoretic maximum entropy (MaxEnt) approach to canonical ensemble is mathematically equivalent to the classic approach of Boltzmann, Gibbs and Darwin-Fowler. The two approaches, however, "interpret" a same mathematical theorem differently; most notably observing mean-energy in the former and energy conservation in the latter. However, applying the same MaxEnt method to grand canonical ensemble fails; while carefully following the classic approach based on Boltzmann's microcanonical {\em equal probability a priori} produces the correct statistics: One does not need to invoke quantum mechanics; and there is no Gibbs paradox. MaxEnt and related minimum relative entropy principle are based on the mathematical theorem concerning large deviations of rare fluctuations. As a scientific method, it requires classic mechanics, or some other assumptions, to provide meaningful {\em prior distributions} for the expected-value based statistical inference. A naive assumption of uniform prior is not valid in statistical mechanics.

Keywords

Cite

@article{arxiv.1105.4118,
  title  = {Maximum Entropy Principle, Equal Probability a Priori and Gibbs Paradox},
  author = {Hao Ge and Hong Qian},
  journal= {arXiv preprint arXiv:1105.4118},
  year   = {2011}
}

Comments

5 pages, no figures

R2 v1 2026-06-21T18:10:13.082Z