Theoretical characterization of end-on and side-on peroxide coordination in ligated Cu2O2 models


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Cramer C. J. , Kinal A. , Wloch M., Piecuch P., Gagliardi L.

JOURNAL OF PHYSICAL CHEMISTRY A, cilt.110, ss.11557-11568, 2006 (SCI İndekslerine Giren Dergi)

  • Cilt numarası: 110 Konu: 40
  • Basım Tarihi: 2006
  • Doi Numarası: 10.1021/jp064232h
  • Dergi Adı: JOURNAL OF PHYSICAL CHEMISTRY A
  • Sayfa Sayısı: ss.11557-11568

Özet

The relative energetics of mu-eta(1):eta(1) (trans end-on) and mu-eta(2):eta(2) (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.