Electronic state selectivity in dication-molecule single electron transfer reactions: NO2+ + NO

Abstract

The single-electron transfer reaction between NO²⁺ and NO, which initially forms a pair of NO⁺ ions, has been studied using a position-sensitive coincidence technique. The reactivity in this class of collision system, which involves the interaction of a dication with its neutral precursor, provides a sensitive test of recent ideas concerning electronic state selectivity in dicationic single-electron transfer reactions. In stark contrast to the recently observed single-electron transfer reactivity in the analogous CO₂²⁺/CO₂ and O₂²⁺/O₂ collision systems, electron transfer between NO²⁺ and NO generates two product NO⁺ ions which behave in an identical manner, whether the ions are formed from NO²⁺ or NO. This observed behaviour is in excellent accord with the recently proposed rationalization of the state selectivity in dication-molecule SET reactions using simple propensity rules involving one-electron transitions.