DIRECT PUMP-PROBE SPECTROSCOPY OF THE NEAR-IR BAND OF THE SOLVATED ELECTRON IN ALCOHOLS

We report femtosecond direct pump/probe data on the s-state to p-state transition of the solvated electron in alcohols. The data reveal a p- state lifetime of almost-equal-to 0.5 ps and a large spectral componen t due to displacement along the ground-state solvent coordinate involv ing slow diffusive solvent motions and subsequent relaxation. The larg e displacement is surprising considering the short excited-state lifet ime and the long relaxation times of these modes. This effect is appar ently the result of a previously unknown p-state to s-state nonadiabat ic rearrangement of the solvent coordinate of solvated electrons in al cohols.