Isotope effect on hydrated electron relaxation dynamics studied with time-resolved liquid jet photoelectron spectroscopy
Abstract
The excited state relaxation dynamics of the solvated electron in H2O and D2O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H2O and 102 ± 8 fs in D2O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- May 10, 2016
- Source ID
- 10.1063/1.4948546
Entities
People
- Daniel Neumark
- Holly L. Williams
- Madeline H Elkins
Organizations
- Air Force Office of Scientific Research
- German Research Foundation
- Lawrence Berkeley National Laboratory
- National Science Foundation
- University of California