Electronic Resource
College Park, Md.
:
American Institute of Physics (AIP)
The Journal of Chemical Physics
96 (1992), S. 5076-5087
ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
With the help of Monte Carlo simulation techniques, we study the recombination kinetics of hydrated electrons (e−aq) with H3O+ and OH⋅ which results from the photoionization of pure water with femtosecond pulsed lasers. A full description of the simulation procedure is given and various comparisons are made with analytical formulations of the reaction kinetics. Particular attention is given to the reaction of e−aq with H3O+, which is only partially diffusion controlled and which involves a Coulombic interaction with dielectric saturation effects. We find that the probability of reaction per e−aq –H3O+ encounter is small (∼6%) and that the encounter duration can be of the order of a few picoseconds. The competition between the reaction of e−aq with H3O+ and with OH⋅ is analyzed with the simulations and with the independent reaction times method. Both approaches indicate that the e−aq decay is largely dominated by the reaction of e−aq with OH⋅. The effect of neighboring ionization sites on the e−aq decay kinetics is also included in the simulations to account for different possible densities of ionization sites. The initial separation between the reactants is found to be about 1 nm, in agreement with previous determinations. The significance of this last value and the constraints that it puts on the initial kinetic energy of the photoelectrons is discussed.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.462751
Permalink
| Library |
Location |
Call Number |
Volume/Issue/Year |
Availability |
