American Chemical Society
jp064232h_si_001.pdf (441.57 kB)
Download file

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

Download (441.57 kB)
journal contribution
posted on 2006-10-12, 00:00 authored by Christopher J. Cramer, Armagan Kinal, Marta Włoch, Piotr Piecuch, Laura Gagliardi
The relative energetics of μ-η:η1 (trans end-on) and μ-η: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.