title: Covalent bonding in heavy metal oxides.
abstract: Novel theoretical methods were used to quantify the magnitude and the energetic contributions of 4f/5f-O2p and 5d/6d-O2p interactions to covalent bonding in lanthanide and actinide oxides. Although many analyses have neglected the involvement of the frontier d orbitals, the present study shows that f and d covalencies are of comparable importance. Two trends are identified. As is expected, the covalent mixing is larger when the nominal oxidation state is higher. More subtly, the importance of the nf covalent mixing decreases sharply relative to (n + 1)d as the nf occupation increases. Atomic properties of the metal cations that drive these trends are identified.
authors.affiliation: Department of Chemistry and the Center for Advanced Scientific Computing and Modeling, University of North Texas, Denton, Texas 76203-5017, USA.
authors.forename: Paul S
authors.identifier: 0000000349315217
authors.initials: PS
authors.lastname: Bagus
authors.affiliation: Consultant, Austin, Texas 78730, USA.
authors.forename: Connie J
authors.initials: CJ
authors.lastname: Nelin
authors.affiliation: Department of Chemistry and the Center for Advanced Scientific Computing and Modeling, University of North Texas, Denton, Texas 76203-5017, USA.
authors.forename: Dave A
authors.identifier: 0000000332940470
authors.initials: DA
authors.lastname: Hrovat
authors.affiliation: Pacific Northwest National Laboratory, Richland, Washington 99352, USA.
authors.forename: Eugene S
authors.initials: ES
authors.lastname: Ilton