Materials discovery by chemical analogy: role of oxidation states in structure prediction

Abstract

The likelihood of an element to adopt a specific oxidation state in a solid, given a certain set of neighbours, might often be obvious to a trained chemist. However, encoding this information for use in high-throughput searches presents a significant challenge. We carry out a statistical analysis of the occurrence of oxidation states in 16 735 ordered, inorganic compounds and show that a large number of cations are only likely to exhibit certain oxidation states in combination with particular anions. We use this data to build a model that ascribes probabilities to the formation of hypothetical compounds, given the proposed oxidation states of their constituent species. The model is then used as part of a high-throughput materials design process, which significantly narrows down the vast compositional search space for new ternary metal halide compounds. Finally, we employ a machine learning analysis of existing compounds to suggest likely structures for a small subset of the candidate compositions. We predict two new compounds, MnZnBr₄ and YSnF₇, that are thermodynamically stable according to density functional theory, as well as four compounds, MnCdBr₄, MnRu₂Br₈, ScZnF₅ and ZnCoBr₄, which lie within the window of metastability.