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On the Nature of the Bonding in 1:1 Adducts of O2

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journal contribution
posted on 01.12.2003, 00:00 by Dimitrios A. Pantazis, John E. McGrady
A survey of the potential energy surface for a 1:1 copper dioxygen complex, (C3N2H5)CuO2, reveals two distinct states in the valence region, a singlet (1A1) and a triplet (3B1). The former spans a continuum from CuIII−O22- to CuI−O2(1Δg), while the latter spans CuII−O21- to CuI−O2(3Σg-). The point at which the potential energy curves for the two states cross marks an abrupt discontinuity in electron distribution, where the system shifts from dominant CuIII−O22- character to CuII−O21-. On this basis, we argue that there is no continuum between CuIII−peroxide and CuII−superoxide:  the two are represented by distinct states that differ both in symmetry and multiplicity.