Fundamental-measure free-energy density functional for hard spheres: Dimensional crossover and freezing

Abstract

A geometrically based fundamental-measure free-energy density functional unified the scaled-particle and Percus-Yevick theories for the hard-sphere fluid mixture. It has been successfully applied to the description of simple (``atomic'') three-dimensional (3D) fluids in the bulk and in slitlike pores, and has been extended to molecular fluids. However, this functional was unsuitable for fluids in narrow cylindrical pores, and was inadequate for describing the solid. In this work we analyze the reason for these deficiencies, and show that, in fact, the fundamental-measure geometrically based theory provides a free-energy functional for 3D hard spheres with the correct properties of dimensional crossover and freezing. After a simple modification of the functional, as we propose, it retains all the favorable D=3 properties of the original functional, yet gives reliable results even for situations of extreme confinements that reduce the effective dimensionality D drastically. The modified functional is accurate for hard spheres between narrow plates (D=2), and inside narrow cylindrical pores (D=1), and it gives the exact excess free energy in the D=0 limit (a cavity that cannot hold more than one particle). It predicts the (vanishingly small) vacancy concentration of the solid, provides the fcc hard-sphere solid equation of state from closest packing to melting, and predicts the hard-sphere fluid-solid transition, all in excellent agreement with the simulations.