Ion-imaging of the photodissociation of CF3I+

The photodissociation of CF3I+ prepared by resonance enhanced multiphoton ionization has been studied by using velocity-map ion imaging and photoelectron spectroscopy. Photodissociation of CF3I+ between 300 and 306 nm results in dissociation to both CF3+I+ and CF3++I. As in an earlier study using time-of-flight mass spectrometry [L. D. Waits , J. Chem. Phys. 97, 7263 (1992)], the latter channel displays a bimodal velocity distribution, indicative of two different dissociation mechanisms. Photoelectron spectra presented here indicate that, contrary to the earlier suggestion, these dissociation processes must both occur following excitation to the A (2)A(1) state or to another dissociative state of the ion, and the ion images are consistent with this conclusion. The photoelectron angular distributions extracted from the ion images also provide new perspective on earlier studies of the dissociative ionization of CF3I. (C) 2003 American Institute of Physics.