title: Competition of electron transfer, dissociation, and bond-forming processes in the reaction of the CO(2)(2+) dication with neutral CO(2).
abstract: The bimolecular reactivity of the CO(2)(2+) dication with neutral CO(2) is investigated using triple quadrupole and ion-ion coincidence mass spectrometry. Crucial for product analysis is the use of appropriate isotope labelling in the quadrupole experiments in order to distinguish the different reactive pathways. The main reaction corresponds to single-electron transfer from the neutral reagent to the dication, i.e. CO(2)(2+) + CO(2) --> 2CO(2)(+); this process is exothermic by almost 10 eV, if ground state monocations are formed. Interestingly, the results indicate that the CO(2)(+) ion formed when the dication accepts an electron dissociates far more readily than the CO(2)(+) ion formed from the neutral CO(2) molecule. This differentiation of the two CO(2)(+) products is rationalized by showing that the population of the key dissociative states of the CO(2)(+) monocation will be favoured from the CO(2)(2+) dication rather than from neutral CO(2). In addition, two bond-forming reactions are observed as minor channels, one of which leads to CO(+) and O(2)(+) as ionic products and the other affords a long-lived C(2)O(3)(2+) dication.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, Prague 6, Czech Republic.
authors.forename: Claire L
authors.initials: CL
authors.lastname: Ricketts
authors.forename: Detlef
authors.initials: D
authors.lastname: Schröder
authors.forename: Jana
authors.initials: J
authors.lastname: Roithová
authors.forename: Helmut
authors.initials: H
authors.lastname: Schwarz
authors.forename: Roland
authors.initials: R
authors.lastname: Thissen
authors.forename: Odile
authors.initials: O
authors.lastname: Dutuit
authors.forename: Jan
authors.initials: J
authors.lastname: Zabka
authors.forename: Zdenek
authors.initials: Z
authors.lastname: Herman
authors.forename: Stephen D
authors.initials: SD
authors.lastname: Price