Dipole-Bound State, Photodetachment Spectroscopy, and Resonant Photoelectron Imaging of Cryogenically-Cooled 2-Cyanopyrrolide.

Abstract

Valence-bound anions with polar neutral cores can have diffuse dipole-bound excited states just below the electron detachment threshold. Because of the similarity in geometry and vibrational frequencies between the dipole-bound states (DBSs) and the corresponding neutrals, DBSs have been exploited as intermediate states to conduct resonant photoelectron spectroscopy (PES), resulting in highly non-Franck-Condon photoelectron spectra via vibrational autodetachment and providing much richer vibrational information than conventional PES. Here, we report a photodetachment and high-resolution photoelectron imaging study of the 2-cyanopyrrolide anion, cooled in a cryogenic ion trap. The electron affinity of the 2-cyanopyrrolyl radical is measured to be 3.0981 ± 0.0006 eV (24 988 ± 5 cm-1). A DBS is observed for 2-cyanopyrrolide at 240 cm-1 below its detachment threshold using photodetachment spectroscopy. Twenty-three above-threshold vibrational resonances (Feshbach resonances) of the DBS are observed. Resonant PES is conducted at each Feshbach resonance, yielding a wealth of vibrational information about the 2-cyanopyrrolyl radical. Resonant two-photon PES confirms the s-like dipole-bound orbital and reveals a relatively long lifetime of the bound zero-point level of the DBS. Fundamental frequencies for 19 vibrational modes (out of a total of 24) are obtained for the cyanopyrrolyl radical, including six out-of-plane modes. The current work provides important spectroscopic information about 2-cyanopyrrolyl, which should be valuable for the study of this radical in combustion or astronomical environments.