Structural and electronic properties of the sodium tetrasilicate glass Na${}_2$Si${}_4$O${}_9$ from classical and ab initio molecular-dynamics simulations

Abstract

The structure and the electronic properties of a sodium tetrasilicate (Na${}_2$Si${}_4$O${}_9$) glass were studied by combined Car-Parrinello and classical molecular-dynamics simulations. The glass sample was prepared using a method employed recently in a study of a silica glass [M. Benoit {\it et al}, Euro. Phys. J. B {\bf 13}, 631 (2000)]. First we generated a NS4 glass by classical molecular-dynamics and then we took it as the initial configuration of a first-principles molecular-dynamics simulation. In the {\it ab initio} molecular-dynamics simulation, the electronic structure was computed in the framework of the Kohn-Sham density functional theory within the generalized gradient approximation using a B-LYP functional. The Car-Parrinello dynamics is remarkably stable during the considered trajectory and, as soon as it is swit ched on, some significant structural changes occur. The {\it ab initio} description improves the comparison of the structural characteristics with experimental data, in particular concerning the Si-O and Na-O bond lengths. From an electronic point of view, we find that the introduction of the sodium oxide in the silica network lowers the band gap and leads to a highly non-localized effect on the charges of the network atoms.