A fully tetrahedral and highly corner-sharing network model of ZnCl glass and its comparison to SiO glass.

Zinc chloride, ZnCl, is intermediate between a strong and a fragile glass former. During computational simulations, it is therefore important to account for ion polarizability. This, together with the lack of suitable interatomic potential parameters, is the likely cause for the lack of modeling studies on ZnCl glass which contain a high degree of ZnCl tetrahedral units. Through using accurate interatomic potential parameters and applying the adiabatic core-shell model, the first fully tetrahedral model of ZnCl glass was obtained. The Cl-Zn-Cl bond angle of 109° reproduced the ideal tetrahedral bond angle, and the calculated total neutron and x-ray structure factors closely replicated experimental findings. While 86% of the ZnCl tetrahedral units were corner-sharing, 14% were found to be edge-sharing. This led to two distinct contributions in both the Zn-Cl-Zn bond angle distribution and in the Zn⋯Zn nearest neighbour peaks being seen. These are not apparent in studies based on neutron diffraction. By comparing the intermediate glass former ZnCl to the strong glass former SiO, marked differences in ring statistics became apparent. The Zn-Cl-Zn bond angle of around 110° enabled 3-membered rings to form in significant proportions. In contrast, 3-membered rings were only present in SiO glass as defects. By calculating the ZnCl and SiO partial structure factors, strong similarities became visible after scaling according to nearest neighbour distances. Although it was apparent that the main contributions to the first sharp diffraction peak (FSDP) came from cation-anion correlations, the relative scaling of the FSDP positions in ZnCl and SiO glass was not understood.