The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu 2O2 systems

Per Åke Malmqvist, Kristine Pierloot, Abdul Rehaman Moughal Shahi, Christopher J. Cramer, Laura Gagliardi

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Abstract

A multireference second-order perturbation theory using a restricted active space self-consistent field wave function as reference (RASPT2/RASSCF) is described. This model is particularly effective for cases where a chemical system requires a balanced orbital active space that is too large to be addressed by the complete active space self-consistent field model with or without second-order perturbation theory (CASPT2 or CASSCF, respectively). Rather than permitting all possible electronic configurations of the electrons in the active space to appear in the reference wave function, certain orbitals are sequestered into two subspaces that permit a maximum number of occupations or holes, respectively, in any given configuration, thereby reducing the total number of possible configurations. Subsequent second-order perturbation theory captures additional dynamical correlation effects. Applications of the theory to the electronic structure of complexes involved in the activation of molecular oxygen by mono- and binuclear copper complexes are presented. In the mononuclear case, RASPT2 and CASPT2 provide very similar results. In the binuclear cases, however, only RASPT2 proves quantitatively useful, owing to the very large size of the necessary active space.

Original languageEnglish (US)
Article number204109
JournalJournal of Chemical Physics
Volume128
Issue number20
DOIs
StatePublished - 2008

Bibliographical note

Funding Information:
P.Å.M. thanks the Swedish Research Council for Grant No. 621-2004-4122; L.G. and A.R.M.S. thank the Swiss National Science Foundation Grant No. 200021-111645/1; K.P. thanks the Flemish Science Foundation (FWO) and the Concerted Research Action of the Flemish Government (GOA); C.J.C. thanks U.S. NSF Grant No. CHE06-10183. The authors thank Professor B. O. Roos, Lund University, for stimulating discussion on the topic.

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