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Theoretical Characterization of End-on and Side-on Peroxide Coordination in Ligated Cu2O2 Models

Cramer, C. J.; Kinal, A.; Wloch, M.; Piecuch, P.; Gagliardi, L.
J. Phys. Chem. A 2006, 110, 11557.

The relative energetics of μ-η11 (trans end-on) and μ-η22 (side-on) peroxo isomers of Cu2O2 fragments supported by 0, 2, 4, and 6 ammonia ligands have been computed with various density functional, coupled-cluster, and multiconfigurational protocols. There is substantial disagreement between the different levels for most cases, although completely renormalized coupled-cluster methods appear to offer the most reliable predictions. The significant biradical character of the end-on peroxo isomer proves problematic for the density functionals, while the demands on active space size and the need to account for interactions between different states in second-order perturbation theory prove challenging for the multireference treatments. In the latter case, it proved impossible to achieve any convincing convergence.

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