Reaction of the N Atom with Electronically Excited O2 Revisited: A Theoretical Study.

Abstract

The kinetics of the reaction of N with electronically excited O2 (singlet a1Δg and b1Σg+ states), potentially relevant for NOx formation in nonthermal air plasma, is theoretically studied using the multireference second-order perturbation theory. The corresponding thermodynamically and kinetically favored reaction pathways together with possible intersystem crossings are identified. It has been revealed that the energy barrier for the N + O2(a1Δg) → NO + O reaction is approximately twice the barrier height for the counterpart process with O2(X3Σg-). The molecular oxygen in the b1Σg+ state, in turn, proved to be even less reactive to atomic nitrogen than O2(a1Δg). Appropriate thermal rate constants for specified reaction channels are calculated by the variational transition-state theory incorporating corrections for the tunneling effect, nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. The corresponding three-parameter Arrhenius expressions for the broad temperature range (T = 300-4000 K) are reported. At last, post-transition-state molecular dynamics simulations indicate that the N + O2(a1Δg) reaction produces vibrationally much colder NO molecules than the N + O2(X3Σg-) process.