title: Correlated wavefunction methods in bioinorganic chemistry.
abstract: In this commentary the challenges faced in the application of wavefunction-based ab initio methods to (open-shell) transition metal complexes of (bio)inorganic interest are briefly touched on. Both single-reference and multireference methods are covered. It is stressed that the generation and nature of the reference wavefunction is a subject of major importance. How erroneous results can be easily obtained even with coupled-cluster theory is illustrated through the example of the septet-quintet separation in iron(IV)-oxo complexes. Second, the interplay between relativistic and correlation effects is important. This is demonstrated with coupled-cluster calculations on models for dinuclear copper active sites, where relativity has a major influence on the relative stabilities of the bis(μ-oxo) and side-on peroxo species.
authors.affiliation: Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstr 12, 53115, Bonn, Germany. neese@thch.uni-bonn.de
authors.forename: Frank
authors.initials: F
authors.lastname: Neese
authors.forename: Dimitrios G
authors.initials: DG
authors.lastname: Liakos
authors.forename: Shengfa
authors.initials: S
authors.lastname: Ye
mesh_terms: D015393:Chemistry, Bioinorganic; D003198:Computer Simulation; D056831:Coordination Complexes / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry; D011789:Quantum Theory; D028561:Transition Elements / Q000737:chemistry
chemical_list: D056831:Coordination Complexes; D028561:Transition Elements; D003300:Copper; D010100:Oxygen