Photoelectron spectroscopy of deprotonated benzonitrile

The recent discovery of cyano-substituted aromatic and two-ring polycyclic aromatic hydrocarbon molecules in Taurus Molecular Cloud-1 has prompted questions on how the electronic structure and excited-state dynamics of these molecules are linked with their existence and abundance. Here, we report a photodetachment and frequency- and angle-resolved photoelectron spectroscopy study of jet-cooled para-deprotonated benzonitrile (p-[Bzn-H]⁻). The adiabatic detachment energy was determined as 1.70 ± 0.01 eV, in good agreement with CCSD(T)/aug-cc-pVTZ calculations. The spectra across the first few electron-volts above threshold are dominated by prompt autodetachment processes associated with excitation of at least five short-lived (tens of femtoseconds) temporary anion shaped resonances since excitation cross sections are several orders of magnitude larger than direct photodetachment cross sections. The photoexcitation vibronic profile is dominated by a ≈640 cm−1 ring deformation mode. [Bzn-H]⁻ lacks a valence-localized excited state situated below the detachment threshold and does not exhibit thermionic emission following excitation of the temporary anion resonances. Thus, [Bzn-H]⁻ is unlikely to be stable in many interstellar environments.