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.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Jun 15, 2015
- Source ID
- 10.1063/1.4922441
Entities
People
- Daniel Neumark
- Holly L. Williams
- Madeline H Elkins
Organizations
- Air Force Office of Scientific Research
- Lawrence Berkeley National Laboratory
- National Science Foundation
- University of California