Rationalization of the Hubbard U parameter in CeOx from first principles: Unveiling the role of local structure in screening

Abstract

The density functional theory (DFT)+U method has been widely employed in theoretical studies on various ceria systems to correct the delocalization bias in local and semi-local DFT functionals with moderate computational cost. We present a systematic and quantitative study, aiming to gain better understanding of the dependence of Hubbard U on the local atomic arrangement. To rationalize the Hubbard U of Ce 4f, we employed the first principles linear response method to compute Hubbard U for Ce in ceria clusters, bulks, and surfaces. We found that the Hubbard U varies in a wide range from 4.3 eV to 6.7 eV, and exhibits a strong correlation with the Ce coordination number and Ce-O bond lengths, rather than the Ce 4f valence state. The variation of the Hubbard U can be explained by the changes in the strength of local screening due to O → Ce intersite transitions.