Convergence rate of the excess-free-energy functional expansion of a solid about a coexisting liquid

Publisher Website
Google Scholar
Abstract
A recently derived free-energy model for the inhomogeneous hard-sphere fluid yields analytic, easily calculable expressions for the three-particle direct-correlation functions, in good agreement with extensive Monte Carlo simulations near freezing densities. This enables one to perform a systematic study of the convergence rate of the first terms in the density-functional expansion from a reference uniform fluid state to solidlike density distributions. We find that the convergence is too slow to provide a rationale for a density-functional theory of freezing based on the truncated second-order expansion.