Cavity-water interface is polar

Abstract

We present the results of numerical simulations of the electrostatics and dynamics of water hydration shells surrounding Kihara cavities given by a Lennard-Jones (LJ) layer at the surface of a hard-sphere cavity. The local dielectric response of the hydration layer substantially exceeds that of bulk water, with the magnitude of the dielectric constant peak in the shell increasing with the growing cavity size. The polar shell propagates into bulk water to approximately the cavity radius. The statistics of the electrostatic field produced by water inside the cavity follow linear response and approach the prediction of continuum electrostatics with increasing cavity size.