title: Statistical modeling of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2.
abstract: The rates of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2 are modeled by statistical rate theory accounting for energy- and angular momentum-specific rate constants for formation of the primary and secondary cationic adducts and their backward and forward reactions. The reactions are both suggested to proceed on sextet and quartet potential energy surfaces with efficient, but probably not complete, equilibration by spin-inversion of the populations of the sextet and quartet adducts. The influence of spin-inversion on the overall reaction rate is investigated. The differences of the two reaction rates mostly are due to different numbers of entrance states (atom + linear rotor or linear rotor + linear rotor, respectively). The reaction Fe(+) + N2O was studied either with (6)Fe(+) or with (4)Fe(+) reactants. Differences in the rate constants of (6)Fe(+) and (4)Fe(+) reacting with N2O are attributed to different contributions from electronically excited potential energy surfaces, such as they originate from the open-electronic shell reactants.
authors.affiliation: Max-Planck-Institut für Biophysikalische Chemie, Am Fassberg 11, D-37077 Göttingen, Germany. shoff@gwdg.de.
authors.forename: Vladimir G
authors.initials: VG
authors.lastname: Ushakov
authors.forename: Jürgen
authors.initials: J
authors.lastname: Troe
authors.forename: Ryan S
authors.initials: RS
authors.lastname: Johnson
authors.forename: Hua
authors.initials: H
authors.lastname: Guo
authors.forename: Shaun G
authors.initials: SG
authors.lastname: Ard
authors.forename: Joshua J
authors.initials: JJ
authors.lastname: Melko
authors.forename: Nicholas S
authors.initials: NS
authors.lastname: Shuman
authors.forename: Albert A
authors.initials: AA
authors.lastname: Viggiano
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D002248:Carbon Monoxide / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008956:Models, Chemical; D009589:Nitrogen Oxides / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D009589:Nitrogen Oxides; D002245:Carbon Dioxide; D002248:Carbon Monoxide; D007501:Iron