Metastable anions of dinitrobenzene: Resonances for electron attachment and kinetic energy release

Attachment of free, low-energy electrons to dinitrobenzene (DNB) in the gas phase leads to DNB − as well as several fragment anions. DNB − , (DNB-H) − , (DNB-NO) − , (DNB-2NO) − , and (DNB-NO 2 ) − are found to undergo metastable (unimolecular) dissociation. A rich pattern of resonances in the yield of these metastable reactions versus electron energy is observed; some resonances are highly isomer-specific. Most metastable reactions are accompanied by large average kinetic energy releases (KER) that range from 0.5 to 1.32 eV, typical of complex rearrangement reactions, but (1,3-DNB-H) − features a resonance with a KER of only 0.06 eV for loss of NO. (1,3-DNB-NO) − offers a rare example of a sequential metastable reaction, namely, loss of NO followed by loss of CO to yield C 5 H 4 O − with a large KER of 1.32 eV. The G4(MP2) method is applied to compute adiabatic electron affinities and reaction energies for several of the observed metastable channels.