Assessing Hubbard-corrected AM05+U and PBEsol+U density functionals for strongly correlated oxides CeO2 and Ce2O3

Abstract

The structure–property relationships of bulk CeO₂ and Ce₂O₃ have been investigated using AM05 and PBEsol exchange–correlation functionals within the frameworks of Hubbard-corrected density functional theory (DFT+U) and density functional perturbation theory (DFPT+U). Compared with conventional PBE+U, RPBE+U, PW91+U and LDA+U functionals, AM05+U and PBEsol+U describe experimental crystalline parameters and properties of CeO₂ and Ce₂O₃ with superior accuracy, especially when +U is chosen close to its value derived by the linear-response approach. The present findings call for a reexamination of some of the problematic oxide materials featuring strong f- and d-electron correlation using AM05+U and PBEsol+U.