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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

Huber, S. M.; Moughal Shahi, A. R.; Aquilante, F.; Cramer, C. J.; Gagliardi, L.
J. Chem. Theor. Comput. 2009, 5, 2967 (doi:10.1021/ct00282m).

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) offered similar accuracy with significantly reduced computational overhead provided an inner (2,2) complete active space was included in the overall RAS space to account for strong biradical character in most of the compounds. The effects of different active space choices and outer RAS space excitations are examined and conclusions drawn with respect to the general applicability of the RASPT2 protocol.