Connection Between Thermodynamics and Dynamics of Simple Fluids in Pores: Impact of Fluid-Fluid Interaction Range and...

Using molecular simulations, we investigate how the range of fluid-fluid (adsorbate-adsorbate) interactions and the strength of fluid-solid (adsorbate-adsorbent) interactions impact the strong connection between distinct adsorptive regimes and distinct self-diffusivity regimes reported in [Krekelberg, W. P.; Siderius, D. W.; Shen, V. K.; Truskett, T. M.; Errington, J. R. Langmuir2013, 29, 14527-14535]. Although increasing the fluid-fluid interaction range changes both the thermodynamics and the dynamic properties of adsorbed fluids, the previously reported connection between adsorptive filling regimes and self-diffusivity regimes remains. Increasing the fluid-fluid interaction range leads to enhanced layering and decreased self-diffusivity in the multilayer-formation regime but has little effect on the properties within film-formation and pore-filling regimes. We also find that weakly attractive adsorbents, which do not display distinct multilayer formation, are hard-sphere-like at super- and subcritical temperatures. In this case, the self-diffusivity of the confined and bulk fluid has a nearly identical scaling-relationship with effective density.