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Title: Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

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:
;  [1] ;  [1] ;  [2]
  1. Department of Chemistry, University of California, Berkeley, California 94720 (United States)
  2. (United States)
Publication Date:
OSTI Identifier:
22415987
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 23; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; EXCITATION; EXCITED STATES; INTERNAL CONVERSION; LIFETIME; LIQUIDS; METHANOL; PHOTOELECTRON SPECTROSCOPY; PROBES; RECOMBINATION; RELAXATION; SOLVATED ELECTRONS; SOLVATION; SOLVENTS; TIME RESOLUTION; TRANSIENTS