Experimental and Theoretical Insights into the Structure of Tellurium Chloride Glasses

Abstract : The structure of the binary chalcohalide glasses TeCl (0.35 ≤ x ≤ 0.65) is considered by combining experimental and theoretical results. The structural network properties are influenced by a competition between ionic and covalent bonding in such glasses. At first, a focus is placed on the detailed information available by using the complementary high-energy X-ray and the neutron diffractions in both the reciprocal and real spaces. The main characteristic suggested by the structure factors S( Q) concerns the presence of three length scales in the intermediate range order. The total correlation function T( r) lets us also suppose that the structure of these glasses is more complicated than Te-chain fragments with terminal Cl as demonstrated in crystalline TeCl. Molecular dynamics simulations were subsequently performed on TeCl and TeCl, and coupled with the experimental data, a highly reticulated network of chalcogen atoms, with a fair amount of chlorine atoms bonded in a bridging mode, is proposed. The simulations clearly lead to a glass description that differs markedly from the simple structural model based on only Te atom chains and terminal Cl atoms. Solid-state NMR experiments and NMR parameters calculations allowed validation of the presence of Te highly coordinated with chlorine in these glasses.