A reactive molecular dynamics simulation of the silica-water interface.

ABSTRACT

We report our study of a silica-water interface using reactive molecular dynamics. This first-of-its-kind simulation achieves length and time scales required to investigate the detailed chemistry of the system. Our molecular dynamics approach is based on the ReaxFF force field of van Duin et al. [J. Phys. Chem. A 107, 3803 (2003)]. The specific ReaxFF implementation (SERIALREAX) and force fields are first validated on structural properties of pure silica and water systems. Chemical reactions between reactive water and dangling bonds on a freshly cut silica surface are analyzed by studying changing chemical composition at the interface. In our simulations, reactions involving silanol groups reach chemical equilibrium in approximately 250 ps. It is observed that water molecules penetrate a silica film through a proton-transfer process we call "hydrogen hopping," which is similar to the Grotthuss mechanism. In this process, hydrogen atoms pass through the film by associating and dissociating with oxygen atoms within bulk silica, as opposed to diffusion of intact water molecules. The effective diffusion constant for this process, taken to be that of hydrogen atoms within silica, is calculated to be 1.68 x 10(-6) cm(2)/s. Polarization of water molecules in proximity of the silica surface is also observed. The subsequent alignment of dipoles leads to an electric potential difference of approximately 10.5 V between the silica slab and water.