B3LYP calculations of cerium oxides.
In this paper we evaluate the performance of density functional theory with the B3LYP functional for calculations on ceria (CeO(2)) and cerium sesquioxide (Ce(2)O(3)). We demonstrate that B3LYP is able to describe CeO(2) and Ce(2)O(3) reasonably well. When compared to other functionals, B3LYP performs slightly better than the hybrid functional PBE0 for the electronic properties but slightly worse for the structural properties, although neither performs as well as LDA+U(U=6 eV) or PBE+U(U=5 eV). We also make an extensive comparison of atomic basis sets suitable for periodic calculations of these cerium oxides. Here we conclude that there is currently only one type of cerium basis set available in the literature that is able to give a reasonable description of the electronic structure of both CeO(2) and Ce(2)O(3). These basis sets are based on a 28 electron effective core potential (ECP) and 30 electrons are attributed to the valence space of cerium. Basis sets based on 46 electron ECPs fail for these materials.
Materials Chemistry, The Angström Laboratory, Uppsala University, Box 538, S-751 21 Uppsala, Sweden.
Jolla
J
Kullgren
Christopher W M
CW
Castleton
Carsten
C
Müller
David Muñoz
DM
Ramo
Kersti
K
Hermansson