The entropic origin of the enhancement of liquid diffusion close to a neutral confining surface.

It is known that, in the proximity of a neutral wall, liquids experience diffusion enhancement relative to their bulk diffusion, but the origin of this phenomenon is still unknown. We report a molecular dynamics simulation investigating the dynamics of a simple liquid in the proximity to a non-interacting smooth confining wall, which exhibits a strong diffusion enhancement within the liquid layers adjacent to the wall. We present an analysis of these results, demonstrating that the observed diffusion enhancement can be accounted for, with numerical accuracy, using the universal scaling law that relates the liquid diffusion rate to the excess entropy. These results show that the scaling law, which has so far only been used for the description of the bulk liquid diffusion, can be successfully used to describe the diffusion in liquids under nano-scale confinement.
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