A perturbative density functional theory for square-well fluids

摘要

We report a perturbative density functional theory for quantitative description of the structural and thermodynamic properties of square-well fluids in the bulk or at inhomogeneous conditions. The free-energy functional combines a modified fundamental measure theory to account for the short-range repulsion and a quadratic density expansion for the long-range attraction. The long-correlation effects are taken into account by using analytical expressions of the direct correlation functions of bulk fluids recently obtained from the first-order mean-spherical approximation. The density functional theory has been calibrated by extensive comparison with simulation data from this work and from the literature. The theory yields good agreement with simulation results for the radial distribution function of bulk systems and for the density profiles of square-well fluids near the surfaces of spherical cavities or in slit pores over a broad range of the parameter space and thermodynamic conditions.