Cation disorder is an important design criterion for technologically relevant transition-metal (TM) oxides, such as radiation-tolerant ceramics and Li-ion battery electrodes. In this letter, we use a combination of first-principles calculations, normal mode analysis, and band-structure arguments to pinpoint a specific electronic-structure effect that influences the stability of disordered phases. We find that the electronic configuration of a TM ion determines to which extent the structural energy is affected by site distortions. This mechanism explains the stability of disordered phases with large ionic radius differences and provides a concrete guideline for the discovery of novel disordered compositions.
@article{arxiv.1710.05097,
title = {The electronic-structure origin of cation disorder in transition-metal oxides},
author = {Alexander Urban and Aziz Abdellahi and Stephen Dacek and Nongnuch Artrith and Gerbrand Ceder},
journal= {arXiv preprint arXiv:1710.05097},
year = {2017}
}