Modeling inhomogeneous van der Waals fluids using an analytical direct correlation function

Yiping Tang and Jianzhong Wu
Phys. Rev. E 70, 011201 – Published 23 July 2004

Abstract

Rosenfeld’s perturbative method [J. Chem. Phys. 98, 8126 (1993)] for constructing the Helmholtz energy functional of classical systems is applied to studying inhomogeneous Lennard-Jones fluids, in which the key input—the bulk direct correlation function—is obtained from the first-order mean-spherical approximation (FMSA) [J. Chem. Phys. 118, 4140 (2003)]. Preserving its high fidelity at the bulk limit, the FMSA shows stable and satisfactory performance for a variety of inhomogeneous Lennard-Jones fluids including those near hard walls, inside slit pores, and around colloidal particles. In addition, the inhomogeneous FMSA reproduces reliably the radial distribution function at its bulk limit. The FMSA is found, in particular, much better than the mean-field theory for fluids near hard surfaces. Unlike alternative non-mean-field approaches, the FMSA is computationally as efficient as the mean-field theory, free of any numerical determination of structure information, weight functions, or empirical parameters.

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  • Received 16 January 2004

DOI:https://doi.org/10.1103/PhysRevE.70.011201

©2004 American Physical Society

Authors & Affiliations

Yiping Tang*

  • Honeywell Process Solutions, 300-250 York Street, London, Ontario, Canada N6A 6K2

Jianzhong Wu

  • Department of Chemical and Environmental Engineering, University of California, Riverside, California 92521-0425, USA

  • *Corresponding author.Email address: yiping.tang@honeywell.com

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Vol. 70, Iss. 1 — July 2004

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