Prolonged Association between Water Molecules under Hydrophobic Nanoconfinement.

Abstract

We present an investigation of the dynamics of water confined among rigid carbon rods and between parallel graphene sheets with molecular dynamics simulations. Diffusion coefficients, activation energy of diffusion, and residence-time correlation functions as a function of confinement geometry reveal a retardation of water dynamics under hydrophobic confinement compared to bulk water. In fact, water under various confinements possesses longer associations with its neighbors and exhibits diffusion dynamics characteristic of a lower temperature. Analysis of the residence-time correlation functions reveals long and short residence times, which we relate to the diffusion coefficient and activation energy of diffusion, respectively. Additional investigations reveal how the level of confining surface hydrophobicity affects water dynamics, further broadening our understanding of water diffusion inside diverse media. Overall, this study sheds light on the physical origin of retarded water dynamics under hydrophobic confinement and the close relationship between residence times and diffusion behavior.