Ionospheric chemistry: Theoretical treatment of ONOO+ and of NO3+

Abstract

In light of accurate ab initio calculations, we discuss the charge transfer, vibrational and electronic de-excitations between O2/O 2+ + NO+/NO and O/ O+ + NO 2+ / NO2 through the formation and decomposition of NO3+ and ONOO+. For that purpose, we generated the potentials of the electronic ground and excited states of the colliding and molecular species involved in these reactions. We used configuration interaction methods and a large basis set. We predict multistep pathways, which involve both the long range and the molecular regions of the potential energy surfaces of the electronic states of the stable isomers of NO3+ and those of the weakly bound charge transfer complex ONOO+. The couplings between these electronic states such as vibronic, Renner-Teller, Jahn-Teller, and spin orbit are believed to play crucial roles during these important ionospheric ion-molecule reactions. © 2009 American Institute of Physics.