Exploration of Entropy Pair Functional Theory

Abstract

Evaluation of the entropy from molecular dynamics (MD) simulation remains an out-standing challenge. The standard approach requires thermodynamic integration across a series of simulations. Recent work Nicholson et al. demonstrated the ability to construct a functional that returns excess entropy, based on the pair correlation function (PCF); it was capable of providing, with acceptable accuracy, the absolute excess entropy of iron simulated with a pair potential in both fluid and crystalline states. In this work, the general applicability of the Entropy Pair Functional Theory (EPFT) approach is explored by applying it to three many-body interaction potentials. These potentials are state of the art for large scale models for the three materials in this study: Fe modelled with a modified embedded atom method (MEAM) potential, Cu modelled with an MEAM and Si modelled with a Tersoff potential. We demonstrate the robust nature of EPFT in determining excess entropy for diverse systems with many-body interactions. These are steps toward a universal Entropy Pair Functional, EPF, that can be applied with confidence to determine the entropy associated with sophisticated optimized potentials and first principles simulations of liquids, crystals, engineered structures, and defects.