Density functional theory for Baxter’s sticky hard spheres in confinement.

Hansen-Goos, H.; Miller, M.A.; Wettlaufer, J.S.

Abstract

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.

Citation

Hansen-Goos, H., Miller, M., & Wettlaufer, J. (2012). Density functional theory for Baxter’s sticky hard spheres in confinement. Physical Review Letters, 108(4), Article 047801. https://doi.org/10.1103/physrevlett.108.047801

• Journal Article Type: Article
• Publication Date: 2012-01
• Deposit Date: Apr 11, 2013
• Journal: Physical Review Letters
• Print ISSN: 0031-9007
• Electronic ISSN: 1079-7114
• Publisher: American Physical Society
• Peer Reviewed: Peer Reviewed
• Volume: 108
• Issue: 4
• Article Number: 047801
• DOI: https://doi.org/10.1103/physrevlett.108.047801