In this work, we demonstrate the mechanism by which electronic charge localization increases the chemical expansion coefficient in two model systems, CeO2−δ and BaCeO3−δ. Using Density Functional Theory calculations, we predict that this coefficient is increased by more than 70% when charge is fully localized, consistent with the observation that materials with a smaller degree of charge localization have smaller chemical expansion coefficients. This finding has important consequences for devising materials with smaller chemical expansion coefficients and for the reliability of the widely-used Shannon's ionic radii.
Physical Chemistry Chemical Physics
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