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

Journal Article · Sun Jun 21 04:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4922441· OSTI ID:22415987

Elkins, Madeline H.; Williams, Holly L. ^[1]; Neumark, Daniel M. ^[1]

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1. Department of Chemistry, University of California, Berkeley, California 94720 (United States)

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.

• OSTI ID: 22415987
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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