Year: 2026
Type: preprint
Abstract: Compositionally complex perovskite oxides provide a broad design space for catalytic materials, yet the electronic consequences of configurational disorder remain insufficiently understood. Here, we use high-throughput density functional theory calculations to systematically investigate how B-site compositional complexity modifies the local electronic structure of perovskite oxides across single-metal, binary, and quinary compositions. We analyze electronic descriptors relevant to catalytic activity, including transition-metal eg occupancy, d-band center, oxygen p-band center, and metal–oxygen d–p overlap. Based on data mining of DFT electronic structures for 4,035 compositionally disordered perovskites, we demonstrate that configurational disorder gives rise to distributions of local electronic states originating from heterogeneous coordination environments. As a result, transition metals with electronic and oxidation-state flexibility can access substantially broadened electronic configurations. Compositional complexity also expands the range of accessible metal–oxygen interactions, although the magnitude and direction of this effect vary among constituent elements. These results establish a distribution-based description of electronic structure for compositionally disordered perovskites and highlight local-environment statistics as a key dimension for understanding and tuning the catalytic electronic structure of disordered oxides.
Source: ChemRxiv
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7213456271