title: Simple, unambiguous theoretical approach to oxidation state determination via first-principles calculations.
abstract: We introduce a novel theoretical approach for determining oxidation states (OS) from quantum-mechanical calculations. For a transition-metal ion, for example, the metal-ligand orbital mixing contribution to the charge allocated to the ion is separated from that due to the actual occupation of the d-orbitals from which OS can then be inferred. We report the application of this approach to different transition-metal systems: molecular complexes, ruthenium-dye molecules, ruthenium complexes with noninnocent ligands, and bulk semiconductors. The computations were carried out using density-functional theory with a Hubbard U correction. The oxidation states were determined without ambiguity.
authors.affiliation: Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA. hsit@princeton.edu
authors.forename: Patrick H-L
authors.initials: PH
authors.lastname: Sit
authors.forename: Roberto
authors.initials: R
authors.lastname: Car
authors.forename: Morrel H
authors.initials: MH
authors.lastname: Cohen
authors.forename: Annabella
authors.initials: A
authors.lastname: Selloni
mesh_terms: D008024:Ligands; D008956:Models, Chemical; D010084:Oxidation-Reduction; D011789:Quantum Theory; D028561:Transition Elements / Q000737:chemistry
chemical_list: D008024:Ligands; D028561:Transition Elements