title: Nucleophilic substitution with two reactive centers: The CN(-) + CH3I case.
abstract: The nucleophilic substitution reaction CN(-) + CH3I allows for two possible reactive approaches of the reactant ion onto the methyl halide, which lead to two different product isomers. Stationary point calculations predict a similar shape of the potential and a dominant collinear approach for both attacks. In addition, an H-bonded pre-reaction complex is identified as a possible intermediate structure. Submerged potential energy barriers hint at a statistical formation process of both CNCH3 and NCCH3 isomers at the experimental collision energies. Experimental angle- and energy differential cross sections show dominant direct rebound dynamics and high internal excitation of the neutral product. No distinct bimodal distributions can be extracted from the velocity images, which impedes the indication of a specific preference towards any of the product isomers. A forward scattering simulation based on the experimental parameters describes accurately the experimental outcome and shows how the possibility to discriminate between the two isomers is mainly hindered by the large product internal excitation.
authors.affiliation: Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria.
authors.forename: E
authors.initials: E
authors.lastname: Carrascosa
authors.affiliation: Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria.
authors.forename: M
authors.initials: M
authors.lastname: Bawart
authors.affiliation: Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria.
authors.forename: M
authors.initials: M
authors.lastname: Stei
authors.affiliation: Department of Physics, AlbaNova, Stockholm University, 10691 Stockholm, Sweden.
authors.forename: F
authors.initials: F
authors.lastname: Linden
authors.affiliation: Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria.
authors.forename: F
authors.initials: F
authors.lastname: Carelli
authors.affiliation: Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria.
authors.forename: J
authors.initials: J
authors.lastname: Meyer
authors.affiliation: Department of Physics, AlbaNova, Stockholm University, 10691 Stockholm, Sweden.
authors.forename: W D
authors.initials: WD
authors.lastname: Geppert
authors.affiliation: Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria.
authors.forename: F A
authors.initials: FA
authors.lastname: Gianturco
authors.affiliation: Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria.
authors.forename: R
authors.initials: R
authors.lastname: Wester