title: Theoretical Study of the Dissociation Energy of First-Row Metallocenium Ions.
abstract: The bond dissociation energy of a series of metallocenium ions, i.e., the energy difference of the reaction MCp2(+) → MCp(+) + Cp· (with M = Ti, V, Cr, Mn, Fe, Co, and Ni), was studied by means of multiconfigurational perturbation theory (CASPT2, RASPT2, NEVPT2) and restricted coupled cluster theory (CCSD(T)). From a comparison between the results obtained from these different methods, and a detailed analysis of their treatment of electron correlation effects, a set of MCp(+)-Cp binding energies are proposed with an accuracy of 5 kcal/mol. The computed results are in good agreement with the experimental data measured by threshold photoelectron photoion coincidence (TPEPICO) spectroscopy but disagree with the more recent threshold collision-induced dissociation (TCID) experiments.
authors.affiliation: Department of Chemistry, KU Leuven , Celestijnenlaan 200F, B-3001 Leuven, Flanders, Belgium.
authors.forename: Quan Manh
authors.initials: QM
authors.lastname: Phung
authors.affiliation: Department of Chemistry, KU Leuven , Celestijnenlaan 200F, B-3001 Leuven, Flanders, Belgium.
authors.forename: Steven
authors.initials: S
authors.lastname: Vancoillie
authors.affiliation: Department of Chemistry, KU Leuven , Celestijnenlaan 200F, B-3001 Leuven, Flanders, Belgium.
authors.forename: Kristine
authors.initials: K
authors.lastname: Pierloot