Actinic Wavelength Action Spectroscopy of the IO^- Reaction Intermediate

Iodinate anions are important in the chemistry of the atmosphere where they are implicated in ozone depletion and particle formation. The atmospheric chemistry of iodine is a complex overlay of neutral-neutral, ion-neutral, and photochemical processes, where many of the reactions and intermediates remain poorly characterized. This study targets the visible spectroscopy and photostability of the gas-phase hypoiodite anion (IO^-), the initial product of the I^- + O₃ reaction, by mass spectrometry equipped with resonance-enhanced photodissociation and total ion-loss action spectroscopies. It is shown that IO^- undergoes photodissociation to I^- + O (³P) over 637-459 nm (15700-21800 cm^-1) because of excitation to the bound first singlet excited state. Electron photodetachment competes with photodissociation above the electron detachment threshold of IO^- at 521 nm (19200 cm^-1) with peaks corresponding to resonant autodetachment involving the singlet excited state and the ground state of neutral IO possibly mediated by a dipole-bound state.