Dissociative Photodetachment Dynamics of Isomeric Forms of N3O2

The dissociative photodetachment of N3O2- at 532, 355, and 266 nm has been studied using coincident photoelectron and photofragment translational spectroscopy in a fast-ion beam. The photoelectron spectra confirm previous experimental evidence for a weakly perturbed NO-(N2O) complex and show for the first time a broad continuum at large electron-binding energies. Translational energy release spectra exhibit both low- and high-energy-release channels, indicating that two regions of the NO−N2O neutral potential energy surface with very different intermolecular repulsion are accessed. Photoelectron−photofragment coincidence data confirm that the high translational energy release events are correlated with the continuum in the photoelectron spectrum. These dissociative photodetachment dynamics are consistent with the existence of two isomeric species, an ion−dipole complex with the charge localized on the NO moiety and a molecular anion with an estimated stability of 2.0 ± 0.2 eV relative to NO + N2O + e-.