On thermodynamic stability and ensemble equivalence at phase coexistence

TL;DR

This paper revisits classical thermodynamic theory to include interface effects at phase coexistence, resolving ensemble inequivalence and convexity issues, and accurately predicting surface tension through simulations.

Contribution

It extends Hill's 1960s theory to incorporate interface free energy, restoring convexity and ensemble equivalence in phase coexistence analysis.

Findings

Restores convexity of thermodynamic potentials in coexistence regions.

Achieves convergence of grandcanonical and canonical ensemble results.

Accurately predicts surface tension consistent with Onsager's theory.

Abstract

Numerical simulations of systems at coexistence are known to yield unstable fields in some regions of the density parameters, as well as inequivalence of ensembles. The Van der Waals-like loops are attributed to effects of the interface between the coexisting phases, but the question of convexity remains unresolved. We recover the theory developed by Hill in the 1960's, and adapt it to include the interface free energy. Our adapted theory is verified through carefully planned simulations, and gives a thermodynamic description of the interface behaviour inside the coexistence region which restores the proper convexity of the thermodynamic potentials, as well as yields convergence of grandcanonical and canonical results. As a bonus, our interpretation allows direct calculation of surface tension in very good accordance with Onsager's analytic prediction.