Solid-state chemistry of glassy antimony oxides

Abstract

The amorphous phases of antimony oxide at three different oxidation levels have been investigated by {\it ab initio} molecular-dynamics calculations using a simulated `melt-quench' approach. The atomic and electronic structure of the amorphous phases are analyzed and compared to their crystalline counterparts. The amorphous structure of the trioxide ({\it a\,}--Sb$_2$O$_3$) resembles the $\beta$-phase of the crystalline form (valentinite), in agreement with previous observations. In the relaxed athermal structure, however, more senarmontite-like structural features are apparent. The phase diagram of the amorphous phases with respect to oxygen chemical potential has been calculated within the framework of {\it ab initio} thermodynamics. At elevated oxidation levels, the resulting tetraoxide and pentoxide materials show distinct variation in electronic structure compared to the trioxide, with the electronic density of states indicating a narrowing of the electronic gap with increasing oxidation level.