Ro-vibrational Distribution of NO⁺ Dissociated from NO₂⁺ Ions in the a³B₂ and b³A₂ States: A Slow “Impulsive” Dissociation Example Revealed from Threshold Photoelectron–Photoion Coincidence Imaging

Abstract

To clarify the contentions about dissociative photoionization mechanism of nitrogen dioxide via the a3B2 and b3A2 ionic states, a new threshold photoelectron–photoion coincidence (TPEPICO) velocity imaging has been conducted in the 12.8–14.0 eV energy range at the Hefei Light Source. The fine vibrational-resolved threshold photoelectron spectrum agrees well with the previous measurements. The ro-vibrational distributions of NO+, as the unique fragment ion in the dissociation of NO2 + in specific vibronic levels of a3B2 and b3A2 states, are derived from the recorded TPEPICO velocity images. A “cold” vibrational (v + = 0) and “hot” rotational population is observed at the a3B2(0,3,0) and (0,4,0) vibronic levels, while the dissociation of NO2 + in b3A2(0,0,0) leads to the NO+ fragment with both hot vibrational and rotational populations. With the aid of the quantum chemical calculations at the time-dependent B3LYP level, minimum energy paths on the potential energy surfaces of the a3B2 and b3A2 states clarify their adiabatic dissociation mechanisms near the thresholds, and this study proposes reliable explanations for the observed internal energy distributions of fragment ions. Additionally, this study provides valuable insights into the application of the classical “impulsive” model on an overall slow dissociation process.