A three dimensional integral equation approach for fluids under confinement: Argon in zeolites.

In this work, we explore the ability of an inhomogeneous integral equation approach to provide a full three dimensional description of simple fluids under conditions of confinement in porous media. Explicitly, we will consider the case of argon adsorbed into silicalite-1, silicalite-2, and an all-silica analogue of faujasite, with a porous structure composed of linear (and zig-zag in the case of silicalite-1) channels of 5-8 Å diameter. The equation is based on the three dimensional Ornstein-Zernike approximation proposed by Beglov and Roux [J. Chem. Phys. 103, 360 (1995)] in combination with the use of an approximate fluid-fluid direct correlation function furnished by the replica Ornstein-Zernike equation with a hypernetted chain closure. Comparison with the results of grand canonical Monte Carlo/molecular dynamics simulations evidences that the theory provides an accurate description for the three dimensional density distribution of the adsorbed fluid, both at the level of density profiles and bidimensional density maps across representative sections of the porous material. In the case of very tight confinement (silicalite-1 and silicalite-2), solutions at low temperatures could not be found due to convergence difficulties, but for faujasite, which presents substantially larger channels, temperatures as low as 77 K are accessible to the integral equation. The overall results indicate that the theoretical approximation can be an excellent tool to characterize the microscopic adsorption behavior of porous materials.