Russian Journal of Electrochemistry

, Volume 53, Issue 9, pp 1042–1053 | Cite as

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

  • Jeffrey R. Reimers
  • Noel S. Hush
Section 3. Electron Transfer Kinetics and Electrochemical Processes


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.


electron transfer transition state theory cusp catastrophe Born–Oppenheimer breakdown non-adiabatic coupling diabatic surfaces Born–Huang surfaces diagonal coupling 


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Copyright information

© Pleiades Publishing, Ltd. 2017

Authors and Affiliations

  1. 1.Department of Physics and International Centre for Quantum and Molecular StructuresShanghai UniversityShanghaiChina
  2. 2.School of Mathematical and Physical SciencesUniversity of Technology SydneySydneyAustralia
  3. 3.School of Molecular BiosciencesThe University of SydneySydneyAustralia
  4. 4.School of ChemistryThe University of SydneySydneyAustralia

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