Photofragment coincidence imaging of small I-(H2O)n clusters excited to the charge-transfer-to-solvent state.

The photodissociation dynamics of small I-(H2O)n(n=2-5) clusters excited to their charge-transfer-to-solvent (CTTS) states have been studied using photofragment coincidence imaging. Upon excitation to the CTTS state, two photodissociation channels were observed. The major channel (approximately 90%) is a two-body process forming neutral I+(H2O)n photofragments, and the minor channel is a three-body process forming I+(H2O)n-1+H2O fragments. Both processes display translational energy [P(ET)] distributions peaking at ET=0 with little available energy partitioned into translation. Clusters excited to the detachment continuum rather than to the CTTS state display the same two channels with similar P(ET) distributions. The observation of similar P(ET) distributions from the two sets of experiments suggests that in the CTTS experiments, I atom loss occurs after autodetachment of the excited [I(H2O)n-]* cluster or, less probably, that the presence of the excess electron has little effect on the departing I atom.