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

Yiping Tang, Jianzhong Wu
2004 Physical Review E  
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
more » ... geneous 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.
doi:10.1103/physreve.70.011201 pmid:15324042 fatcat:2whqlecwcjhkrmypciyaab4nf4