Dynamics of the Charge-Transfer-to-Solvent States in I⁻(Xe)n Clusters

We have used femtosecond photoelectron spectroscopy to monitor the dynamics associated with the charge-transfer-to-solvent (CTTS) states in I - (Xe) n clusters. We find that the lifetime for the 2 P 1/2 CTTS state increases approximately linearly with cluster size, e.g. 550 ± 50, 700 ± 50, and 1550 ± 200 fs for clusters n = 11, 20, and 38, respectively. These states are determined to decay by spin−orbit autodetachment. In contrast, the 2 P 3/2 CTTS state has a lifetime greater than 225 ps for even the smallest cluster studied, n = 6. No evidence for solvent reorganization is observed in the photoelectron spectra.