Distance dependence of the reaction rate for the reduction of metal cations by solvated electrons: a picosecond pulse radiolysis study |
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Authors: | Schmidhammer Uli Pernot Pascal De Waele Vincent Jeunesse Pierre Demarque Alexandre Murata Shigeo Mostafavi Mehran |
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Affiliation: | Laboratoire de Chimie Physique-ELYSE, UMR8000 CNRS, Université Paris Sud, 91405 Orsay, France. |
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Abstract: | 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. |
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