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Intrinsic Rate Constants k et of Photoinduced Electron Transfer between Anthracene Derivatives and Aromatic Donors: Does the Intersecting‐State Model Challenge Marcus Theory When Confronted with an Archetypal Set of Data?
Author(s) -
Dossot Manuel,
Jacques Patrice
Publication year - 2001
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/1522-2675(20011114)84:11<3446::aid-hlca3446>3.0.co;2-r
Subject(s) - chemistry , anthracene , electron transfer , transfer (computing) , photochemistry , state (computer science) , photoinduced electron transfer , electron , set (abstract data type) , computational chemistry , quantum mechanics , physics , parallel computing , computer science , algorithm , programming language
Intrinsic photoinduced electron transfer (PET) rate constants k et , resorting to classically studied acceptor‐donor couples, are confronted to two theoretical models of electron transfer. At a very exergonic driving force, k et remains on a plateau value centered around 10 11 s −1 . It is shown that the well‐known and widely used Marcus theory fails to account for the data located on this plateau. On the contrary, the basically different approach of the intersecting‐state model (ISM) allows fitting the whole set of data with physically realistic parameters. The possibility is discussed that this success of the ISM over the Marcus model may give hints to explain the lack of an inverted region in forward PET in solution.