Structure and dynamics of amorphous silica surfaces

Abstract

We use molecular dynamics computer simulations to study the equilibrium properties of the surface of amorphous silica. Two types of geometries are investigated: (i) clusters with different diameters (13.5, 19, and 26.5 Å) and (ii) a thin film with thickness 29 Å. We find that the shape of the clusters is independent of temperature and that it becomes more spherical with increasing size. The surface energy is in qualitative agreement with the experimental value for the surface tension. The density distribution function shows a small peak just below the surface, the origin of which is traced back to a local chemical ordering at the surface. Close to the surface the partial radial distribution functions as well as the distributions of the bond–bond angles show features which are not observed in the interior of the systems. By calculating the distribution of the length of the Si–O rings we can show that these additional features are related to the presence of two-membered rings at the surface. The surface density of these structures is around 0.6/nm2, in good agreement with experimental estimates. From the behavior of the mean-squared displacement at low temperatures, we conclude that at the surface the cage of the particles is larger than the one in the bulk. Close to the surface the diffusion constant is somewhat larger than the one in the bulk and with decreasing temperature the relative difference grows. The total vibrational density of states at the surface is similar to the one in the bulk. However, if only the one for the silicon atoms is considered, significant differences are found.