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The critical role of the transition-state cusp diameter in understanding adiabatic and non-adiabatic electron transfer

  • Section 3. Electron Transfer Kinetics and Electrochemical Processes
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Abstract

The equation of Levich and Dogonadze describing the rate of electron-transfer processes in the weak-coupling “non-adiabatic” limit is understood in terms of the properties of general adiabatic electron-transfer theory. The cusp diameter describing the continuous changeover of Born–Oppenheimer adiabatic surfaces from donor-like to acceptor-like character is shown to be the critical property controlling reaction rates and intervalence spectra. Their work is presented in the context of general Born–Oppenheimer breakdown phenomena and linked to the overarching cusp catastrophe.

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Authors and Affiliations

  1. Department of Physics and International Centre for Quantum and Molecular Structures, Shanghai University, Shanghai, 200444, China

    Jeffrey R. Reimers

  2. School of Mathematical and Physical Sciences, University of Technology Sydney, Sydney, NSW, 2007, Australia

    Jeffrey R. Reimers

  3. School of Molecular Biosciences, The University of Sydney, Sydney, NSW, 2006, Australia

    Noel S. Hush

  4. School of Chemistry, The University of Sydney, Sydney, NSW, 2006, Australia

    Noel S. Hush

Authors
  1. Jeffrey R. Reimers
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  2. Noel S. Hush
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Correspondence to Jeffrey R. Reimers.

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This paper is the authors’ contribution to the special issue of Russian Journal of Electrochemistry dedicated to the 100th anniversary of the birth of the outstanding Soviet electrochemist Veniamin G. Levich.

Published in Russian in Elektrokhimiya, 2017, Vol. 53, No. 9, pp. 1169–1182.

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Reimers, J.R., Hush, N.S. The critical role of the transition-state cusp diameter in understanding adiabatic and non-adiabatic electron transfer. Russ J Electrochem 53, 1042–1053 (2017). https://doi.org/10.1134/S1023193517090105

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  • DOI: https://doi.org/10.1134/S1023193517090105

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