Beyond the Rosenfeld Functional: Loop Contributions in Fundamental Measure Theory

Abstract

The Rosenfeld functional provides excellent results for the prediction of the fluid phase of hard convex particle systems but fails beyond the freezing point. The reason for this limitation is the neglect of orientational and distance correlations beyond the particle diameter. In the current article we resolve this restriction and generalize the fundamental measure theory to an expansion in intersection centers. It is shown that the intersection probability of particle systems is described by an algebra, represented by Rosenfeld's weight functions. For subdiagrams of intersection networks we derive vertex functions that provide the building blocks for the free energy functional. Their application is illustrated by deriving the Rosenfeld functional and its leading correction which is exact in the third virial order. Furthermore, the methods are used to derive an approximate functional for the infinite sum over Mayer ring diagrams. Comparing this result to the White Bear mark II functional, we find general agreement between both results.