Charge Distribution Near Oxygen Vacancies in Reduced Ceria

TL;DR

This study investigates the charge distribution around oxygen vacancies in cerium oxides, revealing that excess charge tends to localize farther from vacancies, challenging the standard localized electron model used in DFT calculations.

Contribution

The paper provides a novel analysis of charge distribution in cerium oxides using high-resolution crystal structures and bond valence sum analysis, contradicting common assumptions in the field.

Findings

Charge delocalizes among nearby cerium sites in Ce7O12.

In Ce11O20, charge localizes on next nearest neighbors.

Charge prefers to be farthest from oxygen vacancies.

Abstract

Understanding the electronic charge distribution around oxygen vacancies in transition metal and rare earth oxides is a scientific challenge of considerable technological importance. We show how significant information about the charge distribution around vacancies in cerium oxide can be gained from a study of high resolution crystal structures of higher order oxides which exhibit ordering of oxygen vacancies. Specifically, we consider the implications of a bond valence sum analysis of Ce$_{7}$O$_{12}$ and Ce$_{11}$O$_{20}$. To illuminate our analysis we show alternative representations of the crystal structures in terms of orderly arrays of co-ordination defects and in terms of flourite-type modules. We found that in Ce$_{7}$O$_{12}$, the excess charge resulting from removal of an oxygen atom delocalizes among all three triclinic Ce sites closest to the O vacancy. In Ce$_{11}$O$_{20}$, the charge localizes on the next nearest neighbour Ce atoms. Our main result is that the charge prefers to distribute itself so that it is farthest away from the O vacancies. This contradicts \emph{the standard picture of charge localisation} which assumes that each of the two excess electrons localises on one of the cerium ions nearest to the vacancy. This standard picture is assumed in most calculations based on density functional theory (DFT). Based on the known crystal structure of Pr$_{6}$O$_{11}$, we also predict that the charge in Ce$_{6}$O$_{11}$ will be found in the second coordination shell of the O vacancy. Although this review focuses on bulk cerium oxides our approach to characterising electronic properties of oxygen vacancies and the physical insights gained should also be relevant to surface defects and to other rare earth and transition metal oxides.