title: Reactions within fluorobenzene-ammonia heterocluster ions: experiment and theory.
abstract: Reactions occurring within gas phase fluorobenenze-ammonia heterocluster cations (FC(6)H(5)-(NH(3))(n=1-4)) have been studied through the use of a triple quadrupole mass spectrometer as well as employing density functional theory (DFT). Collision induced dissociation (CID) experiments were conducted in which mass selected cluster ions are accelerated into a cell containing argon gas and the resulting products then subsequently mass analyzed. Two dominate reaction channels are observed. The first is simple evaporative loss of neutral ammonia from the cluster ion. The second involves a substitution reaction occurring within the cluster ion to form the aniline cation, C(6)H(5)NH(2)(+), where the reactivity was found to vary as a function of cluster size. DFT calculations have been performed to both help analyze the structure and the reactivity of these cluster ions. Pronounced differences in activation energies were found that provide an explanation for the observed variation of reactivity as a function of cluster size. An ad hoc model based upon the Arrhenius equation was developed to fit both the experimental collision energy dependence of the reaction and the observed lowering of the reaction barrier to aniline formation as a function of cluster size.
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260-3000, USA.
authors.forename: Kristin
authors.initials: K
authors.lastname: Butterworth
authors.forename: Chi-Tung
authors.initials: CT
authors.lastname: Chiang
authors.forename: Brian
authors.initials: B
authors.lastname: Cunningham
authors.forename: Marek
authors.initials: M
authors.lastname: Freindorf
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Furlani
authors.forename: Robert L
authors.initials: RL
authors.lastname: DeLeon
authors.forename: James F
authors.initials: JF
authors.lastname: Garvey
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D005464:Fluorobenzenes / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D008956:Models, Chemical
chemical_list: D005464:Fluorobenzenes; D007477:Ions; D000641:Ammonia