Fundamental-measure density functional for the fluid of aligned hard hexagons: New insights in fundamental measure theory

Abstract

In this article we obtain a fundamental measure functional for the model of aligned hard hexagons in the plane. Our aim is not just to provide a functional for a new, admittedly academic, model, but to investigate the structure of fundamental measure theory. A model of aligned hard hexagons has similarities with the hard disk model. Both share "lost cases", i.e. admit configurations of three particles in which there is pairwise overlap but not triple overlap. These configurations are known to be problematic for fundamental measure functionals, which are not able to capture their contribution correctly. This failure lies in the inability of these functionals to yield a correct low density limit of the third order direct correlation function. Here we derive the functional by projecting aligned hard cubes on the plane x+y+z=0. The correct dimensional crossover behavior of these functionals permits us to follow this strategy. The functional of aligned hard cubes, however, does not have lost cases, so neither had the resulting functional for aligned hard hexagons. The latter exhibits, in fact, a peculiar structure as compared to the one for hard disks. It depends on a uniparametric family of weighted densities through a new term not appearing in the functional for hard disks. Apart from studying the freezing of this system, we discuss the implications of the functional structure for new developments of fundamental measure theory.