Solvation Dynamics of Electron Produced by Two-Photon Ionization of Liquid Polyols. III. Glycerol

Abstract

The solvation dynamics of excess electrons in glycerol have been measured by the pump-probe femtosecond laser technique at 333 K. The electrons are produced by two-photon absorption at 263 nm. The change in the induced absorbance is followed up to 450 ps in the spectral range from 440 to 720 nm. The transient signals of electron solvation have been analyzed by two kinetic models: a stepwise mechanism and a continuous relaxation model, using a Bayesian data analysis method. The results are compared with those previously published for ethylene glycol (J. Phys. Chem. A 2006, 110, 175) and for propanediols (J. Phys. Chem. A 2007, 111, 4902). From the comparison, it is pointed out that solvation dynamics in glycerol is very fast despite its high viscosity. This is interpreted as the existence of efficient traps for the electrons in glycerol with low potential energy. The small shift of the absorption band of the excess electron indicates that the potential of these traps is very close to that corresponding to the fully solvated electron.