Photoelectron–photofragment coincidence spectroscopy of NO 2−(NO) 1,2: solvation effects of NO on NO 2−

Abstract

A study of the dissociative photodetachment dynamics of N 2O 3 − and N 3O 4 − at 258 nm is reported. Using photoelectron–photofragment coincidence (PPC) spectroscopy, information on the energetics and dissociation dynamics is recorded for both N x O y − species. The results indicate that these anions exist as NO 2 −(NO) 1,2 clusters, and dissociation occurs to form NO and NO 2 products upon photodetachment of the extra electron. It is shown that the energy released in the solvation of NO 2 − with one and two NO molecules is 0.23±0.05 and 0.38±0.05 eV, respectively. The photoelectron spectra show that solvation of NO 2 − by one NO does not significantly affect the electronic structure of the anion. The addition of a second NO to NO 2 −(NO), however, leads to a suppression of photodetachment to the A ̃ 2 B 2 excited state of NO 2 in the NO 2(NO) 2 cluster. The data also suggests that the three-body dissociation process of the larger cluster may occur via a sequential decay mechanism.