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

Stefan M. Huber, Abdul Rehaman Moughal Shahi, Francesco Aquilante, Christopher J. Cramer, Laura Gagliardi

Research output: Contribution to journalArticle

30 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)2967-2976
Number of pages10
JournalJournal of Chemical Theory and Computation
Volume5
Issue number11
DOIs
StatePublished - Nov 2009

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