title: What Active Space Adequately Describes Oxygen Activation by a Late Transition Metal? CASPT2 and RASPT2 Applied to Intermediates from the Reaction of O2 with a Cu(I)-α-Ketocarboxylate.
abstract: Multiconfigurational second-order perturbation theory calculations based on a complete active space reference wave function (CASPT2), employing active spaces of increasing size, are well converged at the level of 12 electrons in 12 orbitals for the singlet-triplet state-energy splittings of three supported copper-dioxygen and two supported copper-oxo complexes. Corresponding calculations using the restricted active space approach (RASPT2) offer similar accuracy with a significantly reduced computational overhead provided an inner (2,2) complete active space is included in the overall RAS space in order to account for strong biradical character in most of the compounds. The effects of the different active space choices and the outer RAS space excitations are examined, and conclusions are drawn with respect to the general applicability of the RASPT2 protocol.
authors.affiliation: Department of Physical Chemistry, University of Geneva, 30, Quai Ernest Ansermet, 1211 Genève, Switzerland and Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431.
authors.forename: Stefan M
authors.initials: SM
authors.lastname: Huber
authors.affiliation: Department of Physical Chemistry, University of Geneva, 30, Quai Ernest Ansermet, 1211 Genève, Switzerland and Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431.
authors.forename: Abdul Rehaman
authors.initials: AR
authors.lastname: Moughal Shahi
authors.affiliation: Department of Physical Chemistry, University of Geneva, 30, Quai Ernest Ansermet, 1211 Genève, Switzerland and Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431.
authors.forename: Francesco
authors.initials: F
authors.lastname: Aquilante
authors.affiliation: Department of Physical Chemistry, University of Geneva, 30, Quai Ernest Ansermet, 1211 Genève, Switzerland and Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Cramer
authors.affiliation: Department of Physical Chemistry, University of Geneva, 30, Quai Ernest Ansermet, 1211 Genève, Switzerland and Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431.
authors.forename: Laura
authors.initials: L
authors.lastname: Gagliardi