Solvation dynamics of electron produced by two-photon ionization of liquid polyols. II. Propanediols

J Phys Chem A. 2007 Jun 14;111(23):4902-13. doi: 10.1021/jp068323q. Epub 2007 May 19.

Abstract

Temporal evolution of transient absorption spectra of electrons produced by two-photon ionization of two isomers, propane-1,2-diol (12PD) and propane-1,3-diol (13PD), with 263 nm femtosecond laser pulses has been studied on picosecond time scale. The two-photon absorption coefficients of 12PD and 13PD at 263 nm were determined to be beta = (2.0 +/- 0.3) x 10(-11) and (2.4 +/- 0.3) x 10(-11) m W(-1), respectively. Time-resolved absorption spectra ranging from 440 to 720 nm have been measured, showing a blue shift for the first tens of picoseconds for both solvents. However, the observed solvation dynamics of electron appears faster in 13PD than in 12PD. The transient signals of electron solvation have then been reconstructed with different models (stepwise mechanism or continuous relaxation model) using a Bayesian data analysis method. Results are discussed, compared with those previously obtained in ethylene glycol (J. Phys. Chem. A 2006, 110, 1705) and corroborate the interpretation, according to which the solvation of electrons is mainly governed by continuous solvent molecular motions.