Structure and dynamics of bioactive phosphosilicate glasses and melts from ab initio molecular dynamics simulations

Ab initio Car-Parrinello molecular dynamics simulations were carried out to investigate the melt precursor of a modified phosphosilicate glass with bioactive properties, and to quench the melt to the vitreous state. The properties of the 3000 K liquid were extensively compared with those of the final glass structure. The melt is characterized by a significant fraction of structural defects small rings, undercoordinated and overcoordinated ions , often combined together. The creation or removal of these coordinative defects in the liquid through Si-O bond formation or dissociation reflects frequent exchanges within the silicate first coordination shell, which in turn dynamically modify the intertetrahedral connectivity of silicate groups. The observed dynamical variation in both the identity and the number of silicate groups linked to a tagged Si Qn speciation are considered key processes in the viscous flow of silicate melts I. Farnan and J. F. Stebbins, Science 265, 1206 1994 . On the other hand, phosphate groups do not show an equally marked exchange activity in the coordination shell, but can still form links with Si. Once formed, these Si-O-P bridges are rather stable, and in fact they are retained in the glass phase obtained after cooling; their formation within the present full ab initio melt-and-quench approach strongly supports their presence in melt-derived phosphosilicate glasses with bioactive applications. On the other hand, the simulations show that the fraction of structural defects rapidly decreases during the cooling, and the glass is essentially free of miscoordinated ions and small rings.