An investigation of free-energy-averaged (coarse-grained) potentials for fluid adsorption on heterogeneous solid surfaces

Abstract

Coarse-grained, two-body fluid–solid potentials provide a simple way to describe the interaction between a fluid molecule and a solid in adsorption theories, and also a means to reduce the computational expense in molecular simulations, compared to those employing full atomistic detail. Here we investigate the applicability of a recently proposed mapping procedure to obtain free-energy-averaged (FEA) fluid–solid interactions for fluids on various heterogeneous surfaces. Methane and graphite are chosen as the fluid and the solid, respectively, and the surface graphene layer is modified to create chemical and geometrical heterogeneities; for the latter surfaces, the FEA mapping is appropriately modified to account for vacancies. Adsorption isotherms and fluid density profiles are obtained by performing grand canonical Monte Carlo (GCMC) simulations for explicit-solid and FEA-potential representations, and are compared to gain insights about the applicability and limitations of the FEA potentials. For solids with homogeneous and chemically heterogeneous surfaces, adsorption isotherms and density profiles obtained using FEA potentials are in good agreement with those obtained using an explicit-solid representation. For surfaces containing vacancies, isotherms and density profiles obtained using the unmodified FEA potential differ significantly from their explicit-surface analogues. When using the FEA potential obtained with the modified mapping procedure some deviations are still seen at very high pressure, however, at low to moderate pressures, agreement is, once again, good.