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Mechanism and kinetics of hydrated electron diffusion

J. Chem. Phys. 129, 054505 (2008); doi:10.1063/1.2964101

Published 5 August 2008

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Kafui A. Tay, François-Xavier Coudert, and Anne Boutin
Laboratoire de Chimie Physique, Université de Paris-Sud, 91405 Orsay Cedex, France
Molecular dynamics simulations are used to study the mechanism and kinetics of hydrated electron diffusion. The electron center of mass is found to exhibit Brownian-type behavior with a diffusion coefficient considerably greater than that of the solvent. As previously postulated by both experimental and theoretical works, the instantaneous response of the electron to the librational motions of surrounding water molecules constitutes the principal mode of motion. The diffusive mechanism can be understood within the traditional framework of transfer diffusion processes, where the diffusive step is akin to the exchange of an extramolecular electron between neighboring water molecules. This is a second-order process with a computed rate constant of 5.0  ps−1 at 298  K. In agreement with experiment the electron diffusion exhibits Arrhenius behavior over the temperature range of 298–400  K. We compute an activation energy of 8.9  kJ  mol−1. Through analysis of Arrhenius plots and the application of a simple random walk model it is demonstrated that the computed rate constant for exchange of an excess electron is indeed the phenomenological rate constant associated with the diffusive process. ©2008 American Institute of Physics
History: Received 9 May 2008; accepted 2 July 2008; published 5 August 2008
Permalink: http://link.aip.org/link/?JCPSA6/129/054505/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.20.Pm
    Chemical rate constants, reaction cross sections, and activation energies
  • 82.20.Hf
    Product distribution in chemical kinetics
  • 82.20.Yn
    Solvent effects on reactivity in chemical kinetics
  • 82.30.Fi
    Ion-molecule, ion-ion, and charge-transfer chemical reactions
  • YEAR: 2008

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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