High-resolution photoelectron imaging and resonant photoelectron spectroscopy via noncovalently bound excited states of cryogenically cooled anions.

Valence-bound anions with polar neutral cores (μ > ∼2.5 D) can support dipole-bound excited states below the detachment threshold. These dipole-bound states (DBSs) are highly diffuse and the weakly bound electron in the DBS can be readily autodetached via vibronic coupling. Excited DBSs can be observed in photodetachment spectroscopy using a tunable laser. Tuning the detachment laser to above-threshold vibrational resonances yields vibrationally enhanced resonant photoelectron spectra, which are highly non-Franck-Condon with much richer vibrational information. This perspective describes recent advances in the studies of excited DBSs of cryogenically cooled anions using high-resolution photoelectron imaging (PEI) and resonant photoelectron spectroscopy (rPES). The basic features of dipole-bound excited states and highly non-Franck-Condon resonant photoelectron spectra will be discussed. The power of rPES to yield rich vibrational information beyond conventional PES will be highlighted, especially for low-frequency and Franck-Condon-inactive vibrational modes, which are otherwise not accessible from non-resonant conventional PES. Mode-selectivity and intra-molecular rescattering have been observed during the vibrationally induced autodetachment. Conformer-specific rPES is possible due to the different dipole-bound excited states of molecular conformers with polar neutral cores. For molecules with μ ≪ 2.5 D or without dipole moments, but large quadrupole moments, excited quadrupole-bound states can exist, which can also be used to conduct rPES.