Probing femtosecond solvation dynamics at the condensed phase-vacuum interface

The photoelectron-induced dissociation of CH{sub 3}Cl adsorbed on top of a multilayer deposit ejects methyl radicals into the gas phase. The kinetic energies of these methyls vary with the identity of the underlying multilayer (H{sub 2}O, hexane, CH{sub 3}Cl), from 0.44 to 0.7 eV at the peak, and are much higher than seen for the gas-phase dissociative electron attachment to this molecule. The additional energy is understood in terms of the effects of the {open_quotes}prompt{close_quotes} solvation (<40fs) on the anionic repulsive curve and suggests a powerful approach to probing it. 21 refs., 8 figs., 1 tab.