Tautomeric forms of azolide anions: Vertical electron detachment energies and Dyson orbitals

Abstract

Several decouplings of the electron propagator, including the relatively new P3+ approximation for the self-energy, have been used to calculate vertical electron detachment energies of tautomeric forms of closed-shell, pentagonal, aromatic anions in which ring carbons without bonds to hydrogens appear. This study extends previous work in which the most stable forms of anionic, five-member rings with one to five nitrogens were considered. Whereas the lowest electron detachment energies sometimes are assigned by Koopmans's theorem results to pi orbital vacancies, electron propagator calculations always obtain sigma orbital vacancies for the ground states of the doublet radicals. Higher electron detachment energies that correspond to excited doublets with pi vacancies also are presented. The predicted transition energies are in good agreement with low-intensity peaks in recent anion photoelectron spectra that have been assigned to less stable, tautomeric forms of these anions.