Microscopic Legendre Transform, Canonical Ensemble and Jaynes’ Maximum Entropy Principle

Abstract

Legendre transform between thermodynamic quantities such as the Helmholtz free energy and entropy plays a key role in the formulation of the canonical ensemble. In the standard treatment, the transform exchanges the independent variable from the system’s internal energy to its conjugate variable—the inverse temperature of the heat reservoir. In this article, we formulate a microscopic version of the transform between the free energy and Shannon entropy of the system, where the conjugate variables are the microstate probabilities and the energies (scaled by the inverse temperature). The present approach gives a non-conventional perspective on the connection between information-theoretic measure of entropy and thermodynamic entropy. We focus on the exact differential property of Shannon entropy, utilizing it to derive central relations within the canonical ensemble. Thermodynamics of a system in contact with the heat reservoir is discussed in this framework. Other approaches, in particular, Jaynes’ maximum entropy principle is compared with the present approach.