A novel weighted density functional theory for adsorption, fluid-solid interfacial tension, and disjoining properties of simple liquid films on planar solid surfaces.
A novel weighted density functional theory (WDFT) for an inhomogeneous 12-6 Lennard-Jones fluid is proposed based on the modified fundamental measure theory for repulsive contribution, the mean-field approximation for attractive contribution, and the first-order mean-spherical approximation with a weighted density for correlation contribution. Extensive comparisons of the theoretical results with molecular simulation and experimental data indicate that the new WDFT yields accurate density profiles, adsorption isotherms, fluid-solid interfacial tensions, as well as disjoining potentials and pressures of simple gases such as argon, nitrogen, methane, ethane, and neon confined in slitlike pores or near graphitic solid surfaces. The present WDFT performs better than the nonlocal density functional theory, which is frequently used in the study of adsorption on porous materials. Since the proposed theory possesses a good dimensional crossover and is able to correctly reduce to two-dimensional case, it performs very well even in very narrow pores. In addition, the present WDFT reproduces very well the supercritical fluid-solid interfacial tensions, whereas the theory of Sweatman underestimates them at high bulk densities. The present WDFT predicts that the increase in the fluid-wall attraction may change the sign of the interfacial tension and hence may make the wall from "phobic" to "philic" with respect to the fluid. The new WDFT is computationally as simple and efficient as the mean-field theory and avoids the second-order direct correlation function as an input. It provides a universal way to construct the excess Helmholtz free-energy functional for inhomogeneous fluids such as Yukawa, square-well, and Sutherland fluids.
Yu
Yang-Xin
YX
Department of Chemical Engineering, Tsinghua University, Beijing 100084, People's Republic of China. yangxyu@mail.tsinghua.edu.cn