Author:

Keywords:

Science & Technology, Physical Sciences, Chemistry, Physical, Physics, Atomic, Molecular & Chemical, Chemistry, Physics, MULTICONFIGURATIONAL PERTURBATION-THEORY, UNIMOLECULAR GAS REACTIONS, SPIN-STATE ENERGETICS, AUXILIARY BASIS-SETS, ANO BASIS-SETS, ATOMS, CHEMISTRY, KINETICS, 0307 Theoretical and Computational Chemistry, 0601 Biochemistry and Cell Biology, 0803 Computer Software, Chemical Physics, 3406 Physical chemistry, 3407 Theoretical and computational chemistry

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.