Short-Range Disorder in TeO₂ Melt and Glass

Abstract

High-resolution X-ray pair distribution functions for molten and glassy TeO₂ reveal coordination numbers <i>n</i>_TeO ≈ 4. However, distinct from the known α-, β-, and γ-TeO₂ polymorphs, there is considerable short-range disorder such that no clear cutoff distance between bonded and nonbonded interactions exists. We suggest that this is similar to disorder in δ-TeO₂ and arises from a broad distribution of asymmetric Te-O-Te bridges, something that we observe becomes increasingly asymmetric with increasing liquid temperature. Such behavior is qualitatively consistent with existing interpretations of Raman scattering spectra, and equivalent to temperature-induced coordination number reduction, for sufficiently large cutoff radii. Therefore, TeO₂ contains a distribution of local environments that are, furthermore, temperature dependent, making it distinct from the canonical single-oxide glass formers. Our results are in good agreement with high-level <i>ab initio</i> cluster calculations.