Electron Solvation in Neat Alcohols 6917

We have performed femtosecond studies of electron solvation in a series of neat linear alcohols. The measured formation time of the solvated electron is consistent with previous studies using solutes. The major character of electron solvation, i.e. the two-state character, is evidenced by the finding of an approximate isosbestic wavelength for methanol at 750 nm. Isotope effects for CH3OH, CH30D, and CD30D as well as chain length effects in slowing the solvation dynamics are attributed to hydroxyl librational and translational motions of the alcohol molecules that form the electron cavity. A slower process was also observed, which is attributed to the cooling of the solvated electron as it "vibrationally" relaxes in the ground electron state. In addition to electrons, an ultrafast transient at early times is clearly resolved, this transient species is attributed to either the neutral excited state or the cation of the alcohol.