Observation of a Symmetry-Forbidden Excited Quadrupole-Bound State

We report the observation of a symmetry-forbidden excited quadrupole-bound state (QBS) in the tetracyanobenzene anion (TCNB^-) using both photoelectron and photodetachment spectroscopies of cryogenically-cooled anions. The electron affinity of TCNB is accurately measured as 2.4695 eV. Photodetachment spectroscopy of TCNB^- reveals selected symmetry-allowed vibronic transitions to the QBS, but the ground vibrational state was not observed because the transition from the ground state of TCNB^- (A symmetry) to the QBS (A symmetry) is triply forbidden by the electric and magnetic dipoles and the electric quadrupole. The binding energy of the QBS is found to be 0.2206 eV, which is unusually large due to strong correlation and polarization effects. A centrifugal barrier is observed for near-threshold autodetachment, as well as relaxations from the QBS vibronic levels to the ground and a valence excited state of TCNB^-. The current study shows a rare example where symmetry selection rules, rather than the Franck-Condon principle, govern vibronic transitions to a nonvalence state in an anion.