title: Theoretical investigation of the gas-phase reactions of CrO(+) with ethylene.
abstract: The potential energy surfaces associated with the reactions of chromium oxide cation (CrO(+)) with ethylene have been characterized using density functional, coupled-cluster, and multireference methods. Our calculations show that the most probable reaction involves the formation of acetaldehyde and Cr(+) via a hydride transfer involving the metal center. Our calculations support previous experimental hypotheses that a four-membered ring intermediate plays an important role in the reactivity of the system. We have also characterized a number of viable reaction pathways that lead to other products, including ethylene oxide. Due to the experimental observation that CrO(+) can activate carbon-carbon bonds, a reaction pathway involving C-C bond cleavage has also been characterized. Since many of the reactions involve a change in the spin state in going from reactants to products, locations of these spin surface crossings are presented and discussed. The applicability of methods based on Hartree-Fock orbitals is also discussed.
authors.affiliation: Department of Chemistry, Villanova University, Villanova, Pennsylvania 19085, USA.
authors.forename: Thomas M
authors.initials: TM
authors.lastname: Scupp
authors.forename: Timothy J
authors.initials: TJ
authors.lastname: Dudley