Abstract
Electron-impact double ionization of nitric acid, HNO 3 has been investigated by using ion–ion coincidence techniques coupled with time-of-flight mass spectrometry. The coincidence spectra show that HNO 3 2+ dissociates via a variety of two- and three-body reactions to form the following pairs of ions: OH + + NO +, O + + NO +, OH + + NO 2 +, O + + HNO 2 +, H + + N +, H + + O +, H + + NO +, and H + + NO 2 +. The experimental data are consistent with the HNO 3 2+ ion decaying to form the observed ion pairs via an initial charge-separating bond cleavage followed by the dissociation of the resulting singly charged ions. Interpretation of the coincidence spectra yields a determination of the excitation energy required to form the lowest energy dicationic state that dissociates to form OH + + NO 2 +. Comparison of this excitation energy with estimated values of the double ionization energy of HNO 3 indicate that this state is probably the ground electronic state of HNO 3 2+ and, hence, these investigations provide a first estimate for the double ionization energy of HNO 3.
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