title: Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent.
abstract: The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA.
authors.forename: Madeline H
authors.initials: MH
authors.lastname: Elkins
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA.
authors.forename: Holly L
authors.initials: HL
authors.lastname: Williams
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA.
authors.forename: Daniel M
authors.initials: DM
authors.lastname: Neumark