We explore the early-time electronic relaxation in NaI aqueous solution
exposed to a short UV laser pulse. Rather than initiating the charge transfer
reaction by resonant photoexcitation of iodide, in the present time-resolved
photoelectron spectroscopy study the charge-transfer-to-solvent (CTTS) states
are populated via electronic excitation above the vacuum level. By analyzing
the temporal evolution of electron yields from ionization of two transient
species, assigned to CTTS and its first excited state, we determine both their
ultrafast population and relaxation dynamics. Comparison with resonant-
excitation studies shows that the highly excited initial states exhibit
similar relaxation characteristics as found for resonant excitation.
Implications for structure and dynamical response of the hydration cage are
discussed