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 ⁶Fe⁺ or with ⁴Fe⁺ reactants. Differences in the rate constants of ⁶Fe⁺ and ⁴Fe⁺ reacting with N₂O are attributed to different contributions from electronically excited potential energy surfaces, such as they originate from the open-electronic shell reactants.