A hierarchical approach to the molecular modeling of diffusion and adsorption at nonzero loading in microporous materials

A new hierarchical approach is presented for the modeling of small molecules at nonzero concentrations in microporous materials. This approach is complementary to other methods recently appearing in the literature; it is targeted for systems with pores that are well defined, large enough to host multiple molecules, and energetically uncorrugated in the interior. Statistical mechanical partition functions are calculated on molecular-level models and used as input to coarse-grained models, to predict both adsorption isotherms and self-diffusion coefficients. Certain physically reasonable simplifying approximations are employed to make the partition functions tractable. The approach is demonstrated on the model system of methane in siliceous zeolite ZK4 at , and the results are judged in comparison to those from traditional grand canonical Monte Carlo and molecular dynamics simulations. The adsorption isotherm is predicted to a high degree of accuracy across a large pressure range. The predicted trends in the self-diffusion coefficient are in qualitative agreement with the molecular dynamics results, but there is some quantitative disagreement at the lowest and highest adsorbate loadings.