Layered Fluid Structure and Anomalous Diffusion under Nanoconfinement

Molecular diffusion under nanoconfinement can differ significantly from diffusion in bulk fluids. Using molecular dynamics simulations and molecular mechanics arguments, we elucidate the effect of layering at the confining boundaries on the self-diffusion of a simple, single-phase, confined fluid. In particular, we show that anomalous diffusion due to layering is controlled by the degree of layering as quantified by the recently proposed Wall number (Wa), which compares the strength of the wall–fluid interaction to the thermal energy. For low Wall numbers, layering is not sufficiently pronounced so as to have a significant effect, whereas for Wa ≳ 1, layering is sufficiently important to have a significant effect on diffusion dynamics. In the latter regime, we find that fluid in the fluid–solid interfacial region tends to exhibit restricted dynamics and may only leave this region via a thermally activated hopping process. We also identify conditions under which diffusivity under confinement can be estimated, to a good approximation level, as a weighted average of the bulk and first-layer region diffusivities, leading to direct expressions quantifying the deviation from bulk behavior in terms of the confinement length scale.