Role of Polarization Interactions in the Formation of Dipole-Bound States.

Abstract

Even though there is a critical dipole moment required to support a dipole-bound state (DBS), how molecular polarizability may influence the formation of DBSs is not well understood. Pyrrolide, indolide, and carbazolide provide an ideal set of anions to systematically examine the role of polarization interactions in the formation of DBSs. Here, we report an investigation of carbazolide using cryogenic photodetachment spectroscopy and high-resolution photoelectron spectroscopy (PES). A polarization-assisted DBS is observed at 20 cm-1 below the detachment threshold for carbazolide, even though the carbazolyl neutral core has a dipole moment (2.2 D) smaller than the empirical critical value (2.5 D) to support a dipole-bound state. Photodetachment spectroscopy reveals nine vibrational Feshbach resonances of the DBS, as well as three intense and broad shape resonances. The electron affinity of carbazolyl is measured accurately to be 2.5653 ± 0.0004 eV (20,691 ± 3 cm-1). The combination of photodetachment spectroscopy and resonant PES allows fundamental frequencies for 14 vibrational modes of carbazolyl to be measured. The three shape resonances are due to above-threshold excitation to the three low-lying electronic states (S1-S3) of carbazolide. Resonant PES of the shape resonances is dominated by autodetachment processes. Ultrafast relaxation from the S2 and S3 states to S1 is observed, resulting in constant kinetic energy features in the resonant PES. The current study provides decisive information about the role that polarization plays in the formation of DBSs, as well as rich spectroscopic information about the carbazolide anion and the carbazolyl radical.