Selected-ion flow tube temperature-dependent measurements for the reactions of O₂⁺ with N atoms and N₂⁺ with O atoms.

Abstract

The temperature variation of rate constants has been measured for the gas phase reactions of the oxycation O2(+) with N atoms and of N2(+) with O atoms from 120 to 400 K using a variable temperature-selected ion flow tube. Measured room temperature rate constants, 0.75 × 10(-10) cm(3) s(-1) (±30%) for O2(+) with N and 1.4 × 10(-10) cm(3) s(-1) (±30%) for N2(+) with O, are in agreement with previously reported values. A temperature dependence of T(-0.7(±0.3)) is observed for the O2(+) + N reaction; however, the N2(+) + O reaction is found to be independent of temperature. Calculations at varying levels of theory were used in tandem with experiments to evaluate likely pathways in potential energy surfaces for the reactions of concern.