Quasi-degenerate states and their dynamics in oxygen deficient reducible metal oxides

Abstract

The physical and chemical properties of oxides are defined by the presence of oxygen vacancies. Experimentally, non-defective structures are almost impossible to achieve due to synthetic constraints. Therefore, it is crucial to account for vacancies when evaluating the characteristics of these materials. The electronic structure of oxygen-depleted oxides deeply differs from that of the native forms, in particular, of reducible metal oxides, where excess electrons can localize in various distinct positions. In this perspective, we present recent developments from our group describing the complexity of these defective materials that highlight the need for an accurate description of (i) intrinsic vacancies in polar terminations, (ii) multiple geometries and complex electronic structures with several states attainable at typical working conditions, and (iii) the associated dynamics for both vacancy diffusion and the coexistence of more than one electronic structure. All these aspects widen our current understanding of defects in oxides and need to be adequately introduced in emerging high-throughput screening methodologies.