Density Profiles and Direct Correlation Functions from Density Functional Theory in Binary Hard-Sphere Crystals: Substitutional Solid and Interstitial Solid Solution

Abstract

We determine the fully resolved equilibrium density profiles for two binary hard-sphere crystal structures using classical density functional theory through the White Bear II functional from fundamental measure theory. While for the substitutional crystal, in which some hard spheres are replaced by spheres of slightly smaller diameter, the density profiles are rather similar to the single-component case (narrow Gaussian peaks centered at fcc lattice sites), we observe a more complex behavior for the case of interstitial solid solutions, where the small species is fairly delocalized in the unit cell. Further, we compute the species-resolved inhomogeneous two-body direct correlation functions, depending on two three-dimensional vectors, for these two types of binary crystals. The large--large components are mainly determined by the vacancy concentration $n_\text{vac}$ and show a characteristic magnitude $\sim 1/n_\text{vac}$. Based on this observation, we propose a simple geometric picture. The components of the direct correlation function involving the small spheres substantially differ in interstitial solid solutions from those of the substitutional crystal.