Distance dependence of the reaction rate for the reduction of metal cations by solvated electrons: a picosecond pulse radiolysis study.
The decay of the solvated electron generated by picosecond electron pulse radiolysis is studied by broad-band transient absorption measurements in ethylene glycol solutions containing decimolar concentrations of Cu(2+), Ni(2+), and Pb(2+) metal cations. Analysis of the nonexponential kinetics of the decays reveals molecular parameters of the electron transfer reaction. It is found that the reaction occurs at long distance for Cu(2+) solutions and is only limited to contact distance in the case of Ni(2+) solutions. The distribution of reaction distance strongly depends on the free enthalpy change of the reactions.
Schmidhammer
Uli
U
Laboratoire de Chimie Physique-ELYSE, UMR8000 CNRS, Université Paris Sud, 91405 Orsay, France.
Pernot
Pascal
P
De Waele
Vincent
V
Jeunesse
Pierre
P
Demarque
Alexandre
A
Murata
Shigeo
S
Mostafavi
Mehran
M