Charge localization increases chemical expansion in cerium-based oxides

Abstract

In this work, we demonstrate the mechanism by which electronic charge localization increases the chemical expansion coefficient in two model systems, CeO_2−δ and BaCeO_3−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.