TY - JOUR
T1 - Theoretical characterization of end-on and side-on peroxide coordination in ligated Cu 2O 2 models
AU - Cramer, Christopher J.
AU - Kinal, Armagan
AU - Włoch, Marta
AU - Piecuch, Piotr
AU - Gagliardi, Laura
PY - 2006/10/12
Y1 - 2006/10/12
N2 - The relative energetics of μ-η 1:η 1 (trans end-on) and μ-η 2:η 2 (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.
AB - The relative energetics of μ-η 1:η 1 (trans end-on) and μ-η 2:η 2 (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.
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U2 - 10.1021/jp064232h
DO - 10.1021/jp064232h
M3 - Article
C2 - 17020270
AN - SCOPUS:33750391653
SN - 1089-5639
VL - 110
SP - 11557
EP - 11568
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 40
ER -