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Updated: Mar 25, 2026

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
Photoelectron Spectroscopy of cis-Nitrous Acid Anion (cis-HONO(-))
Allan M Oliveira1, Julia H Lehman1, Anne B McCoy2
1JILA, and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, United States.
Abstract:
We report photoelectron spectra of cis-HONO(-) formed from an association reaction of OH(-) and NO in a pulsed, plasma-entrainment ion source. The experimental data are assigned to the cis-HONO(-) isomer, which is predicted to be the global minimum on the anion potential energy surface. We do not find evidence for a significant contribution from trans-HONO(-). Electron photodetachment of cis-HONO(-) with 1613, 1064, 532, 355, and 301 nm photons accesses the ground X̃ (1)A' (S0) and excited ã (3)A″ (T1) states of neutral HONO. The photoelectron spectrum resulting from detachment forming cis-HONO (S0) exhibits a long vibrational progression, dominated by overtones and combination bands involving the central O-N stretching and ONO bending vibrations. This indicates that there is a significant change in the central O-N bond length between cis-HONO(-) and cis-HONO (S0). The electron affinity (EA) of cis-HONO is determined to be 0.356(8) eV. We also report the dissociation energy (D0) of cis-HONO(-), forming OH(-) + NO, as 0.594(9) eV, which is a factor of 4 decrease in the central O-N bond strength compared to neutral cis-HONO. The T1 state of cis-HONO is shown to be ∼2.3 eV higher in energy than cis-HONO (S0). Electron photodetachment to form cis-HONO (T1) accesses a transition state along the HO-NO bond dissociation coordinate. The resulting photoelectron spectrum exhibits broad peaks spaced by the terminal N═O stretching frequency. Electronic structure calculations and photoelectron spectrum simulations reported here show very good agreement with the experimental data.
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