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Please use this identifier to cite or link to this item: https://dspace.lboro.ac.uk/2134/2818

Title: A non-Marcus model for electrostatic fluctuations in long range electron transfer
Authors: Fletcher, Stephen
Keywords: Marcus theory
electron transfer theory
reorganisation energy
equivalent circuit
electrostatic fluctuations
Issue Date: 2007
Publisher: © Springer
Citation: FLETCHER, S., 2007. A non-Marcus model for electrostatic fluctuations in long range electron transfer. Journal of Solid State Electrochemistry, 11(7), pp 965-969
Abstract: We propose a new model for the elementary act of electron transfer between two species in solution. The central idea is that the solution in the immediate vicinity of each species may be represented by an equivalent circuit consisting of a Debye circuit shunted by a resistor. Based on this insight, we derive a new formula for the one-dimensional potential energy profile of a coupled donor–acceptor pair at finite (but large) separation d, along a charge-fluctuation reaction co-ordinate, at fixed radii of the transition states. The corresponding reorganisation energy of the reaction is also derived, and it is found to differ from that in the Marcus theory. In particular, the new model predicts that the reorganisation energy is independent of the static dielectric constant of the solution, whereas the old model predicts a strong dependence. The difference is traced to the fact that the Marcus theory omits consideration of the work required to form the charge fluctuations and focuses instead on the work required to localise the charge fluctuations. In general, the equivalent circuit approach permits many of the difficult-to-derive equations of non-equilibrium polarisation theory to be written down by inspection.
Description: This article was published in the journal, Journal of Solid State Electrochemistry. The definitive version is available at: http://dx.doi.org/10.1007/s10008-007-0313-5.
URI: https://dspace.lboro.ac.uk/2134/2818
ISSN: 1432-8488
Appears in Collections:Published Articles (Chemistry)

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