Dielectric constant of water as a function of separation in a slab geometry: A molecular dynamics study

Water in confining geometries shows various anomalous properties related to its structure and dynamics compared with bulk water. Here, the dielectric constant of water as a function of separation in a graphite slab geometry was studied using molecular dynamics simulations. The dielectric constants of water were calculated from the orientational polarization of water molecules when an external electric field was applied parallel and normal to the slabs. The reduction of the dielectric constant of water compared with bulk water can be explained by investigating the structure and dynamics of water in slab geometries. We found a preferred orientation of water molecules in the layer closest to the graphite surface. The self-diffusion coefficient distribution of water molecules along the direction normal to the slabs was also computed. Highly mobile water molecules in the intermediate region were generated by the weak hydrogen bonding produced by the preferred orientation of water molecules in the layer. We concluded that the dielectric constant of water in the slab geometry is lower than that of bulk water because of the reduction of the polarization of water and the highly mobile water molecules in the intermediate region arising from the preferred orientation of water molecules.