Theoretical Characterization of End-on and Side-on Peroxide Coordination in Ligated Cu2O2 Models
Title | Theoretical Characterization of End-on and Side-on Peroxide Coordination in Ligated Cu2O2 Models |
Publication Type | Journal Article |
Year of Publication | 2006 |
Authors | Cramer, CJ, Kinal, A, Wloch, M, Piecuch, P, Gagliardi, L |
Journal | The Journal of Physical Chemistry A |
Volume | 110 |
Issue | 40 |
Pagination | 11557-11568 |
Date Published | 09/15/2006 |
Abstract | The relative energetics of μ-η1:η1 (trans end-on) and μ-η2:η2 (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. |