Structural organization of arsenic selenide liquids: New results from liquid state NMR

Insights into the structure and dynamics of the binary As-Se glass system have been obtained from high-temperature ⁷⁷Se nuclear magnetic resonance (NMR) studies of molten samples. In materials having As contents <20 at.%, dynamic exchange averaging processes are detected and analysed quantitatively by detailed lineshape simulations. At high-temperatures (1.5 × glass transition temperature), only a single averaged ⁷⁷Se NMR signal is observed, whose chemical shift arises from the quantitative distribution of As-Se and Se-Se bonds. A detailed analysis of the compositional dependence reveals a tendency towards chemical ordering, based on the structurally dominant AsSe_3/2 groups. Furthermore, the experimental data serve to differentiate between various intermediate range ordering scenarios and favor a structural description in terms of a network in which AsSe_3/2 and Se_2/2 groups are randomly linked.