ALTERNATIVE MECHANISMS FOR SOLVATION DYNAMICS OF LASER-INDUCED ELECTRONS IN METHANOL

A multiphoton ionization study of neat methanol with subpicosecond 2-e V laser pulses has been previously reported. A hybrid electron solvati on mechanism combining both a stepwise transition between two electron -solvent configuration states and a continuous first-order blue shift of the electron absorption spectra was found to closely fit the experi mental data. If substantial absorption from free electrons is assumed in this spectral region, we find that another model comprising thermal ization prior to a stepwise branching localization without blue-shifti ng spectra fits equally well at all wavelengths. However, these two mo dels display considerable differences between their respective kinetic parameters, especially the electron localization time. Furthermore, f or the nonshifting model, this calculated localization time is conside rably longer than that for electron hydration in neat water. We sugges t independent studies such as ultrafast electron scavenging experiment s before adopting a particular mechanism for electron solvation in met hanol.