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 ≈ 0.5 ps and a large spectral component due to displacement along the ground-state solvent coordinate involving slow diffusive solvent motions and subsequent relaxation. The large displacement is surprising considering the short excited-state lifetime and the long relaxation times of these modes. This effect is apparently the result of a previously unknown p-state to s-state nonadiabatic rearrangement of the solvent coordinate of solvated electrons in alcohols.