Marcus Theory of Electron Transfer

  • Philipp O. J. SchererEmail author
  • Sighart F. Fischer
Part of the Biological and Medical Physics, Biomedical Engineering book series (BIOMEDICAL)


In 1992, Rudolph Marcus received the Nobel Prize for chemistry. His theory is currently the dominant theory of electron transfer in chemistry. Originally Marcus explained outer sphere electron transfer, introducing reorganization energy and electronic coupling to relate the thermodynamic transition state to nonequilibrium uctuations of the medium polarization. We begin with a phenomenological description including diusional motion of the reactands. Then, we apply a simplied model with one reaction coordinate to calculate the reaction rate as a function of reorganization energy and reaction free enthalpy. Next, we apply a continuum model for the dielectric medium and derive the free energy contribution of the non equilibrium polarization quite generally. Reorganization energy and activation energy are calculated and transition state theory is applied to calculate the rate constant. We consider a model system consisting of two spherical reactants to calculate the reorganization energy explicitly and discuss charge separation and charge shift processes. We introduce the energy gap as a reaction coordinate and include inner shell reorganization. Finally, the mutual dependency of the electronic wavefunction and the polarization are discussed within a simple model for charge delocalization and self-trapping.

Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  1. 1.Physikdepartment T38Technische Universität MünchenGarchingGermany

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