Observation and Exploitation of Spin-Orbit Excited Dipole-Bound States in Ion-Molecule Clusters.

We report an observation of spin-orbit excited dipole-bound states (DBSs) in arginine-iodide complexes (Arg·I-) by using temperature-dependent, wavelength-resolved "iodide-tagging" negative ion photoelectron spectroscopy. The observed DBSs are bound to the spin-orbit excited I(2P1/2) level of the neutral Arg·I complex in zwitterionic conformations and identified based on the resonant enhancement due to spin-orbit electronic autodetachment from the I(2P1/2) DBS to the I(2P3/2) neutral ground state. The observed DBS binding energies are correlated to the dipole moments of neutral Arg·I isomers and tautomers. This work thus demonstrates a new and generic spectroscopic approach to identify ion-molecule cluster conformations based on their distinguishable dipole moments.