Observation of a dipole-bound excited state in 4-ethynylphenoxide and comparison with the quadrupole-bound excited state in the isoelectronic 4-cyanophenoxide.

Negative ions do not possess Rydberg states but can have Rydberg-like nonvalence excited states near the electron detachment threshold, including dipole-bound states (DBSs) and quadrupole-bound states (QBSs). While DBSs have been studied extensively, quadrupole-bound excited states have been more rarely observed. 4-cyanophenoxide (4CP) was the first anion observed to possess a quadrupole-bound exited state 20 cm below its detachment threshold. Here, we report the observation of a DBS in the isoelectronic 4-ethynylphenoxide anion (4EP), providing a rare opportunity to compare the behaviors of a dipole-bound and a quadrupole-bound excited state in a pair of very similar anions. Photodetachment spectroscopy (PDS) of cryogenically cooled 4EP reveals a DBS 76 cm below its detachment threshold. Photoelectron spectroscopy (PES) at 266 nm shows that the electronic structure of 4EP and 4CP is nearly identical. The observed vibrational features in both the PDS and PES, as well as autodetachment from the nonvalence excited states, are also found to be similar for both anions. However, resonant two-photon detachment (R2PD) from the bound vibrational ground state is observed to be very different for the DBS in 4EP and the QBS in 4CP. The R2PD spectra reveal that decays take place from both the DBS and QBS to the respective anion ground electronic states within the 5 ns detachment laser pulse due to internal conversion followed by intramolecular vibrational redistribution and relaxation, but the decay mechanisms appear to be very different. In the R2PD spectrum of 4EP, we observe strong threshold electron signals, which are due to detachment, by the second photon, of highly rotationally excited anions resulted from the decay of the DBS. On the other hand, in the R2PD spectrum of 4CP, we observe well-resolved vibrational peaks due to the three lowest-frequency vibrational modes of 4CP, which are populated from the decay of the QBS. The different behaviors of the R2PD spectra suggest unexpected differences between the relaxation mechanisms of the dipole-bound and quadrupole-bound excited states.