title: Multireference ab initio calculations of g tensors for trinuclear copper clusters in multicopper oxidases.
abstract: EPR spectroscopy has proven to be an indispensable tool in elucidating the structure of metal sites in proteins. In recent years, experimental EPR data have been complemented by theoretical calculations, which have become a standard tool of many quantum chemical packages. However, there have only been a few attempts to calculate EPR g tensors for exchange-coupled systems with more than two spins. In this work, we present a quantum chemical study of structural, electronic, and magnetic properties of intermediates in the reaction cycle of multicopper oxidases and of their inorganic models. All these systems contain three copper(II) ions bridged by hydroxide or O(2-) anions and their ground states are antiferromagnetically coupled doublets. We demonstrate that only multireference methods, such as CASSCF/CASPT2 or MRCI can yield qualitatively correct results (compared to the experimental values) and consider the accuracy of the calculated EPR g tensors as the current benchmark of quantum chemical methods. By decomposing the calculated g tensors into terms arising from interactions of the ground state with the various excited states, the origin of the zero-field splitting is explained. The results of the study demonstrate that a truly quantitative prediction of the g tensors of exchange-coupled systems is a great challenge to contemporary theory. The predictions strongly depend on small energy differences that are difficult to predict with sufficient accuracy by any quantum chemical method that is applicable to systems of the size of our target systems.
authors.affiliation: Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001 Heverlee-Leuven, Belgium.
authors.forename: Steven
authors.initials: S
authors.lastname: Vancoillie
authors.forename: Jakub
authors.initials: J
authors.lastname: Chalupský
authors.forename: Ulf
authors.initials: U
authors.lastname: Ryde
authors.forename: Edward I
authors.initials: EI
authors.lastname: Solomon
authors.forename: Kristine
authors.initials: K
authors.lastname: Pierloot
authors.forename: Frank
authors.initials: F
authors.lastname: Neese
authors.forename: Lubomír
authors.initials: L
authors.lastname: Rulísek
mesh_terms: D016000:Cluster Analysis; D003300:Copper / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods*; D008956:Models, Chemical; D008958:Models, Molecular; D010088:Oxidoreductases / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D003300:Copper; D010088:Oxidoreductases
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