title: Reactive processes in gas phase Na(+)-iso-C3H7Cl collisions: experimental guided-ion-beam and ab initio studies of the reactions on the ground singlet potential surface of the system up to 12.00 eV.
abstract: Reactive processes, taking place when sodium ions collide with neutral iso-C(3)H(7)Cl molecules in the 0.02-12.00 eV range of energies in the center of mass frame, have been studied using an octopole radiofrequency guided-ion-beam apparatus developed in our laboratory. A dehydrohalogenation reaction channel leading to Na(C(3)H(6))(+) formation has been observed up to 1.00 eV while another process producing NaHCl(+) continues up to 4.00 eV. Furthermore, C(3)H(7)(+) formation resulting from decomposition of the reactants, ion-molecule adducts, has also been observed as well as its decomposition into C(2)H(3)(+) on increasing collision energy. Cross-section energy dependences for all these reactions have been obtained in absolute units. The ab initio electronic structure calculations have been done at the MP2 level for the colliding system ground singlet potential surface, giving information on the reactive surface main topological features. From the surface reactants side to the products' one, different potential wells and barriers have been characterized and their connectivity along the reaction evolution has been established using the intrinsic-reaction-coordinate method, thus interpreting the dynamical evolution of the reactants' collision complex to products. Experimental results demonstrate that NaHCl(+) can be produced via different channels. Reaction rate constants at 308.2 K for both dehydrohalogenation reactions have been calculated from measured excitation functions. It has been also confirmed that the reactants adduct decomposition giving C(3)H(7)(+) and NaCl takes place on the same potential surface. A qualitative interpretation of the experimental results in terms of ab initio calculations is also given.
authors.affiliation: Departament de Química Física, Facultat de Química, Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/Martí i Franquès, 1, 08028 Barcelona, Spain.
authors.forename: J
authors.initials: J
authors.lastname: Aguilar
authors.forename: J M
authors.initials: JM
authors.lastname: Lucas
authors.forename: J
authors.initials: J
authors.lastname: de Andrés
authors.forename: M
authors.initials: M
authors.lastname: Albertí
authors.forename: D
authors.initials: D
authors.lastname: Bassi
authors.forename: A
authors.initials: A
authors.lastname: Aguilar