Structures of hard-sphere fluids from a modified fundamental-measure theory

Abstract

We reformulate Rosenfeld’s fundamental-measure theory using the excess Helmholtz energy density from the Boublik–Mansoori–Carnahan–Starling–Leland equation of state instead of that from the scaled-particle theory. The new density functional theory yields improved density distributions, especially the contact densities, of inhomogeneous hard-sphere fluids as well as more accurate direct and pair correlation functions of homogeneous hard spheres including those of highly asymmetric mixtures. This new density functional theory will provide an accurate reference for the further development of a statistical-thermodynamic theory of complex fluids at uniform and at inhomogeneous conditions.