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The Rehm–Weller Experiment in View of Distant Electron Transfer
Author(s) -
Rosspeintner A.,
Kattnig D. R.,
Angulo G.,
Landgraf S.,
Grampp G.
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200701841
Subject(s) - electron transfer , marcus theory , quenching (fluorescence) , acetonitrile , plateau (mathematics) , electron , chemistry , transfer (computing) , chemical physics , thermodynamics , atomic physics , fluorescence , kinetics , physics , reaction rate constant , quantum mechanics , computer science , mathematics , organic chemistry , mathematical analysis , parallel computing
The driving‐force dependence of bimolecular fluorescence quenching by electron transfer in solution, the Rehm–Weller experiment, is revisited. One of the three long‐standing unsolved questions about the features of this experiment is carefully analysed here, that is, is there a diffusional plateau? New experimental quenching rates are compiled for a single electron donor, 2,5‐bis(dimethylamino)‐1,3‐benzenedicarbonitrile, and eighteen electron acceptors in acetonitrile. The data are analysed in the framework of differential encounter theory by using an extended version of the Marcus theory to model the intrinsic electron‐transfer step. Only by including the hydrodynamic effect and the solvent structure can the experimental findings be well modelled. The diffusional control region, the “plateau”, reveals the inherent distance dependence of the reaction, which is shown to be a general feature of electron transfer in solution.