Počet záznamů: 1

Multireference Ab Initio Calculations of g tensors for Trinuclear Copper Clusters in Multicopper Oxidases

  1. 1.
    0346283 - UOCHB-X 2011 RIV US eng J - Článek v odborném periodiku
    Vancoillie, S. - Chalupský, Jakub - Ryde, U. - Solomon, E. I. - Pierloot, K. - Neese, F. - Rulíšek, Lubomír
    Multireference Ab Initio Calculations of g tensors for Trinuclear Copper Clusters in Multicopper Oxidases.
    Journal of Physical Chemistry B. Roč. 114, č. 22 (2010), s. 7692-7702 ISSN 1520-6106
    Grant CEP: GA MŠk LC512
    Výzkumný záměr: CEZ:AV0Z40550506
    Klíčová slova: g tensors * trinuclear copper clusters * multireference calculations * multicopper oxidases
    Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
    Impakt faktor: 3.603, rok: 2010

    A quantum chemical study of structural, electronic, and magnetic properties of intermediates in the reaction cycle of multicopper oxidases and of their inorganic models has been carried out. 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.
    Trvalý link: http://hdl.handle.net/11104/0005967