Solid–liquid interfacial free energy of small colloidal hard-sphere crystals

Abstract

Using free-energy calculations on small crystalline clusters, we estimate the free-energy density γSL for the solid–liquid equimolar interface of a system of hard-sphere colloids. By studying the behavior of a crystallite at coexistence, we determine the dependence of γSL on the radius of curvature of the interface. An extrapolation to infinite radius of curvature (flat interface), yields γSL(R → ∞) = 0.616(3), in good agreement with recent numerical estimates. Subsequently, we consider the dependence of the interfacial free-energy density on the degree of supersaturation. Our simulations suggest that the γSL associated with the equimolar surface is fairly insensitive to changes in supersaturation.