Atomic scale network structure of a barium aluminosilicate glass doped with different concentrations of rare-earth ions explored by molecular dynamics simulations

Molecular dynamics (MD) simulation is employed for exploring the coordination of atoms in peralkaline BaOAl2O3-SiO2 glasses of variable Gd3+ doping concentrations between 1 and 3.8 mol% Gd2O3. For this the MD simulation procedure of inherent structure sampling was used which provides statistically robust information on the local atomic surrounding of the doped rare earth ions. Distributions of Si/Al/Ba/Gd cations in the first, second and third coordination spheres are investigated. Special focus is laid on the effect of Gd3+ doping concentration on the local surrounding of the Gd3+ ions, i. e. rare earth clustering, and general glass structure. The simulations show that Si-O-Al bonds are preferred in comparison to Si-O-Si and Al-O-Al connections with respect to the random model predictions. Deviations from a statistical Si/Al distribution around the BaOp and GdOq polyhedra are observed. The network modifier ions are preferably surrounded by other network modifier ions, rather than by network formers. It is shown that the incorporation of Gd does not affect radial distribution functions, cumulative radial distribution function curves and the coordination sphere of Gd for Gd2O3 doping concentrations of up to 3.8 mol%, i.e. no rare earth clustering is observed. However, increasing Gd2O3 concentrations decrease the number of bridging oxygen and increase the number of non-bridging oxygen (NBO) species in the glass structure. Charge compensation of the additional non-bridging oxygen species is achieved by increasing NBO coordination numbers with Ba2+.