Density Functional Theory for Baxter’s Sticky Hard Spheres in Confinement

Kurzfassung

It has recently been shown that a free energy for Baxter’s sticky hard-sphere fluid is uniquely defined within the framework of fundamental measure theory (FMT) for the inhomogeneous hard-sphere fluid, provided that it obeys scaled-particle theory and the Percus-Yevick (PY) result for the direct correlation function [ H. Hansen-Goos and J. S. Wettlaufer J. Chem. Phys. 134 014506 (2011)]. Here, combining FMT weighted densities with a new vectorial weighted density, we regularize the divergences of the associated strongly confined limit. The free energy that emerges is exact in the zero-dimensional limit, leaves the underlying equation of state unaffected, and yields a direct correlation function distinct from that of PY. Comparison with simulation data for both the bulk pair-correlation function and the density profiles in confinement shows that the new theory is significantly more accurate than the PY-based results.