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The Role of Solvent Dynamics in Inter- and Intramolecular Electron Exchange Reactions

  • G. Grampp
  • B. Herold
  • C. Shohoji
  • S. Steenken
Conference paper

Abstract

We report on the solvent dynamic effects of inter- and intramolecular electron exchange reactions within organic systems; $$\rm Q_\bullet^{+/-} + Q\ {\mathop{\rightleftharpoons}\ \limits^k}Q + Q_\bullet^{+/-}$$ For a nonadiabatic electron transfer (et) the rate constant k is given by the well known expression: $$k={2\pi{\rm V}_{12}\over \hbar(4\pi \lambda_0 {\rm RT})^{1/2}}\cdot {\rm exp}(-{\lambda_i+\lambda_0\over4{\rm RT}}$$ where V12 denotes the resonance energy splitting. λi is the inner sphere reorganization energy and λ0 stands for the outer sphere reorganization energy, describing the influence of the solvents $$\rm \lambda_0={Z^2e_0^2\ N_L\over 4\pi\ \varepsilon_0}\cdot \big({1\over r}-{1\over d}\big)\cdot αmma$$ where r is the molecular radius, d the reaction distance and γ=(1/n2−1/ε) is the solvent parameter. n, ε are the refractive index and the dielectric constant of the solvent.

Keywords

Dielectric Constant Solvent Parameter Transition State Structure Resonance Split Orbital Model 
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Copyright information

© Springer-Verlag Berlin Heidelberg 1988

Authors and Affiliations

  • G. Grampp
    • 1
  • B. Herold
    • 2
  • C. Shohoji
    • 2
  • S. Steenken
    • 3
  1. 1.Institute of Physical ChemistryUniversity of ErlangenErlangenGermany
  2. 2.Instituto Superior TecnicoLisbonPortugal
  3. 3.MPI für StrahlenchemieMühlheimGermany

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