Статья
2017

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

Jeffrey R. Reimers Jeffrey R. Reimers , Noel S. Hush Noel S. Hush
Российский электрохимический журнал
https://doi.org/10.1134/S1023193517090105
Abstract / Full Text
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

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.

Author information

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

    Jeffrey R. Reimers

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

    Jeffrey R. Reimers

  • School of Molecular Biosciences, The University of Sydney, Sydney, NSW, 2006, Australia

    Noel S. Hush

  • School of Chemistry, The University of Sydney, Sydney, NSW, 2006, Australia

    Noel S. Hush

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