Dissociation Dynamics of Anionic Nitrogen Dioxide in the Low-Lying Resonant States.

Abstract

Experimental studies of the dynamics near the molecular dissociation threshold are frequently frustrated, due to the small cross sections and the demand for identification of close-lying electronic states or nuclear motions with multiple degrees of freedom. Using the high-resolution anion velocity map imaging technique, here we report a dynamics study of the dissociations of anionic nitrogen dioxide in low-lying resonant states formed by electron attachment [e- + NO2 (X2A1) → NO2- → NO (X2Π) + O- (2P)]. The long-term puzzling issues about the near-threshold dissociations of NO2- are settled. We suggest that three low-lying resonant states (1B1, 3B1, and 3B2) of NO2- contribute to the production of O- at attachment energies of <5 eV. Furthermore, B1 and B2 symmetries of the resonant states lead to different anisotropies of the O- angular distribution. At the relatively high electron attachment energies, a prompt fragmentation in the molecular bent conformation competes with an indirect dissociation in the straightened conformation.