Journal of Physical Chemistry A, Vol.114, No.45, 12042-12051, 2010
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 broadband transient absorption measurements in ethylene glycol solutions containing decimolar concentrations of Cu2+, Ni2+, and Pb2+ 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 Cu2+ solutions and is only limited to contact distance in the case of Ni2+ solutions. The distribution of reaction distance strongly depends on the free enthalpy change of the reactions.