Water in porous glasses. A computer simulation Study

We report molecular dynamics simulations of water confined in a cylindrical silica pore. The pore geometry and size is similar to that of typical pores in porous Vycor glass. In the present study we focus on the dependence of microscopical structural and dynamical properties on the degree of hydration of the pore. We have performed five simulations of systems between 19 and 96 % hydration. In all cases, water adsorbs strongly on the pore surface, clearly demonstrating the hydrophilic nature of the Vycor surface. Two layers of water molecules are affected strongly by the interactions with the glass surface. With decreasing degree of hydration an increasing volume in the center of the pore is devoid of water molecules. At 96 % hydration the center is a continuous and homogeneous region that has, however, a lower density than bulk water at ambient conditions. A well-pronounced mobility profile exists, where molecules in the center of the pores have substantially higher self diffusion coefficients than molecules on the pore surface. The spectral densities of center of mass and hydrogen atom motion show the signature of confinement for the molecules close to the pore surface, while the spectral densities in the center of the pore are similar to those in bulk water. The molecular dynamics results are in good agreement with recent experiments. Our data indicate that the dependence of experimental data on the level of hydration of the Vycor sample is due to the different relative contribution of molecules adsorbed on the pore surface and bulk-like molecules in the interior of the pore to the experimental averages. (C) 1999 Elsevier Science B.V. All rights reserved.