The impact of configurational disorder on electronic structure of perovskite oxides
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.
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BibTeX
@misc{kee2026impact,
title = {{The impact of configurational disorder on electronic structure of perovskite oxides}},
author = {Joonyoung Kee and Chuancheng Duan and Kevin Huang and Bin Ouyang},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008957/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008957/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - The impact of configurational disorder on electronic structure of perovskite oxides
AU - Joonyoung Kee
AU - Chuancheng Duan
AU - Kevin Huang
AU - Bin Ouyang
PY - 2026
DA - 2026/09/16
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008957/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008957/v1
AB - 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.
ER -