Water under hydrophobic confinement: entropy and diffusion

TL;DR

This study uses molecular dynamics simulations to show that water exhibits significantly enhanced diffusion near hydrophobic surfaces, and this behavior can be accurately described by a universal entropy-based scaling law.

Contribution

It demonstrates that the entropy-based scaling law for diffusion applies to water under nanoscale hydrophobic confinement, extending its use beyond simple liquids.

Findings

Water diffusion is strongly enhanced near hydrophobic walls.

The entropy scaling law accurately predicts water diffusion in confinement.

Results support the universality of the diffusion-entropy relationship.

Abstract

The properties of liquid water are known to change drastically in confined geometries. A most interesting and intriguing phenomenon is that the diffusion of water is found to be strongly enhanced by the proximity of a hydrophobic confining wall relative to the bulk diffusion. We report a molecular dynamics simulation using a classical water model investigating the water diffusion near a non-interacting smooth confining wall, which is assumed to imitate a hydrophobic surface. A pronounced diffusion enhancement is observed in the water layers adjacent to the wall. We present evidence that the observed diffusion enhancement can be accounted for, with numerical accuracy, using the universal scaling law for liquid diffusion that relates the liquid diffusion rate to the excess entropy. These results show that the scaling law, that has so far only been used for the description of the diffusion in simple liquids, can successfully describe the diffusion in water. It is thus shown that the law can be used for the description of water dynamics under nano-scale confinement which is currently a subject of intense research activity.