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The Marcus Inverted Region from Theory to Experiment
Author(s) -
Grampp Günter
Publication year - 1993
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199306911
Subject(s) - marcus theory , reaction rate constant , intuition , electron transfer , thermodynamics , transfer (computing) , reaction rate , statistical physics , chemistry , physics , classical mechanics , philosophy , kinetics , epistemology , computer science , organic chemistry , parallel computing , catalysis
Electron back‐transfer reactions are the reactions in which the occurrence of the inverted region predicted by the Marcus theory was detected for the first time in an inter molecular electron transfer. In this region, contrary to all intuition, a further increase in the exergonicity causes a decrease in the reaction rate. In each case the forward reactions showed the classical Rehm–Weller behavior the rate constant k approaches k diff of the diffusion‐controlled reaction. This difference has not yet been explained satisfactorily.