Probing the electronic structure and dipole-bound state of the 7-azaindolide anion

We report an investigation of the electronic structure and dipole-bound state (DBS) of the cryogenically-cooled 7-azaindolide anion (7-AI^-) using high-resolution photoelectron imaging, photodetachment spectroscopy, and resonant photoelectron spectroscopy. The electron affinity of the 7-AI radical is measured to be 2.6967(8) eV (21 751 ± 6 cm^-1). Two excited electronic states of the neutral radical are observed at 0.8 eV and 1.4 eV above the ground state. Two minor isomers of 7-AI^- due to deprotonation from the α- and β-carbon on the pyrrole ring are also detected with lower adiabatic detachment energies. A DBS is observed for the 7-AI^- anion at 156 cm^-1 below the detachment threshold, along with 16 vibrational Feshbach resonances. Resonant two-photon photoelectron imaging reveals that the DBS is relatively long-lived. Resonant photoelectron spectroscopy <i>via</i> the vibrational Feshbach resonances of the DBS gives rise to rich vibrational features for the 7-AI radical not accessible in conventional photoelectron spectroscopy. Fundamental vibrational frequencies for 16 vibrational modes of the 7-AI neutral radical are measured experimentally, including 7 bending modes. The current work provides extensive experimental electronic and vibrational information for the 7-AI^- anion and the 7-AI radical.