6533b834fe1ef96bd129d848
RESEARCH PRODUCT
Theoretical characterization of end-on and side-on peroxide coordination in ligated Cu2O2 models.
Piotr PiecuchArmagan KinalMarta WłochLaura GagliardiChristopher J. Cramersubject
Models MolecularCations DivalentInorganic chemistry010402 general chemistry01 natural sciencesPeroxidechemistry.chemical_compoundIsomerismComputational chemistry0103 physical sciencesOrganic chemistryPhysical and Theoretical ChemistryPerturbation theory010304 chemical physicsMolecular Structure010308 nuclear & particles physicsChemistryOxidesGeneral Medicine0104 chemical sciences3. Good healthCharacterization (materials science)PeroxidesQuaternary Ammonium CompoundsActive spaceCharacter (mathematics)Models Chemicalddc:540Copperdescription
The relative energetics of mu-eta1:eta1 (trans end-on) and mu-eta2:eta2 (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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2006-01-01 | The journal of physical chemistry. A |