Kinetics of CO⁺ and CO₂⁺ with N and O atoms

We have measured reaction rate constants for CO⁺ and CO₂⁺ reacting with N and O atoms using a selected ion flow tube apparatus equipped with a microwave discharge atom source. Experimental work was supplemented by molecular structure calculations. Calculated pathways show the sensitivity of kinetic barriers to theoretical methods and imply that high-level ab initio methods are required for accurate energetics. We report room-temperature rate constants of 1.0 ± 0.4 × 10^-11 cm³ s^-1 and 4.0 ± 1.6 × 10^-11 cm³ s^-1 for the reactions of CO⁺ with N and O atoms, respectively, and 8.0 ± 3.0 × 10^-12 cm³ s^-1 and 2.0 ± 0.8 × 10^-11 cm³ s^-1 for the reactions of CO₂⁺ with N and O atoms, respectively. The reaction of CO₂⁺ + O is observed to yield O₂⁺ exclusively. These values help resolve discrepancies in the literature and are important for modeling of the Martian atmosphere.