Chemical potential, Helmholtz free energy and entropy of argon with kinetic Monte Carlo simulation

Abstract

We present a method based on kinetic Monte Carlo (kMC) to determine the chemical potential, Helmholtz free energy and entropy of a fluid within the course of a simulation. The procedure requires no recourse to auxiliary methods to determine the chemical potential, such as the implementation of a Widom scheme in Metropolis Monte Carlo simulations, as it is determined within the course of the simulation. The equation for chemical potential is proved, for the first time in the literature, to have a direct connection with inverse Widom potential theory in using real molecules rather than ghost molecules. We illustrate this new procedure by several examples, including fluid argon and adsorption of argon as a non-uniform fluid on a graphite surface and in slit pores. © 2014 © 2013 Taylor & Francis.