Observation of Core-Excited Dipole-Bound States.

Polar molecules can bind an electron in a diffuse orbital due to the charge-dipole interaction. Electronic excited states of polar molecules can also bind an electron to form core-excited dipole-bound states (DBSs), analogous to core-excited Rydberg states. However, core-excited DBSs have not been observed because of the complicated electronic structure of molecular systems. Here, we report the observation of a core-excited DBS in the pyrazolide anion as a result of the favorable electronic structure of the neutral pyrazolyl core, which has a low-lying excited state (Ã 2 B 1 ) only 266 cm -1 above its ground state (X̃ 2 A 2 ). The binding energy of the DBS associated with the ground state is measured to be 221 cm -1 , while that of the core-excited DBS is 276 cm -1 , which is still a bound state relative to the detachment threshold. Vibrational Feshbach resonances are observed for both DBSs, and their autodetachment behaviors are studied by resonant photoelectron imaging.