Capillary Condensation in Pores with Energetically Heterogeneous Walls: Density Functional versus Monte Carlo Calculations

Abstract

We investigate adsorption of a Lennard–Jones fluid in slit-like pores with energetically heterogeneous walls by using Grand Canonical Monte Carlo simulations and a density functional approach. The model of a fluid-wall potential is qualitatively similar to that invoked by Röcken et al. (J. Chem. Phys.108, 8089, (1999); i.e., it consists of a homogeneous part that varies in the direction perpendicular to the wall and a periodic part, varying also in one direction parallel to the wall, but in contrast to the above mentioned work, both parts of the fluid-wall potential are modeled by Lennard–Jones (9, 3) type functions. The structure of the adsorbed film is characterized by local densities. We evaluate the phase diagrams for several systems characterized by different corrugation of the adsorbing potential and discuss the discrepancies between theoretical predictions and computer simulations.