Analysis of Intrinsic Defects in CeO2 Using a Koopmans-Like GGA+U Approach

Abstract

We have investigated the formation of intrinsic defects in CeO 2 using density functional theory with the generalized gradient approximation (GGA) corrected for on-site Coulombic interactions (GGA+ U ). We employed an ab initio fitting procedure to determine a U {O 2p } value that satisfies a Koopmans-like condition and obtained a value of U {O 2p } = 5.5 eV. We subsequently demonstrated that by applying GGA+ U to the O 2p states, in addition to the Ce 4f states, we were able to model localized holes in addition to localized electrons, thus improving the description of p -type defects in CeO 2 . Our results show that under oxygen-poor conditions the defects with the lowest formation energy are oxygen vacancies, while oxygen interstitials, which form peroxide ions, will be more favorable under oxygen-rich conditions. We carried out temperature and pressure dependence analyses to determine the relative abundance of intrinsic defects under real-world conditions and determined that oxygen vacancies will always be the dominant defect. Furthermore, we determined that at the dilute limit none of the defects studied can account for the intrinsic ferromagnetism that has been observed in nanosized CeO 2 .