Theoretical characterization of end-on and side-on peroxide coordination in ligated Cu 2O 2 models

Christopher J. Cramer, Armagan Kinal, Marta Włoch, Piotr Piecuch, Laura Gagliardi

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72 Scopus citations

Abstract

The relative energetics of μ-η 11 (trans end-on) and μ-η 22 (side-on) peroxo isomers of Cu 2O 2 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.

Original languageEnglish (US)
Pages (from-to)11557-11568
Number of pages12
JournalJournal of Physical Chemistry A
Volume110
Issue number40
DOIs
StatePublished - Oct 12 2006

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