Observation of an Excited Dipole-Bound State in a Diatomic Anion.

We report the observation of σ-type and π-type excited dipole-bound states (DBSs) in cryogenically cooled potassium iodide (KI) anions for the first time. Two DBSs were observed 39.7(10) meV and 5.0(12) meV below the photodetachment threshold via the resonant two-photon detachment. The different photoelectron angular distributions and binding energies suggest that the two DBSs are of different types. The existence of one σ-type and one π-type DBS in the KI anion was also supported by the high-level ab initio theoretical calculations. The excellent agreement between experimental and theoretical results confirms the prediction that a dipolar molecule with a large enough dipole moment can have an excited DBS.