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Free‐Energy Dependence of the Ion Yield of Photo‐Induced Electron‐Transfer Reactions in Solution
Author(s) -
Vauthey Eric,
Suppan Paul,
Haselbach Edwin
Publication year - 1988
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/hlca.19880710111
Subject(s) - chemistry , exergonic reaction , marcus theory , electron transfer , yield (engineering) , ion , electron acceptor , photochemistry , reaction rate constant , acceptor , electron , atomic physics , kinetics , thermodynamics , organic chemistry , condensed matter physics , physics , quantum mechanics , catalysis
Abstract A study of photo‐induced electron‐transfer reactions in MeCN with 9,10‐dicyanoanthracene as acceptor and 21 electron donors with transient photoconductivity measurements is reported. The free‐ion yield and the rate constant of back electron transfer are determined. For exergonic reactions, the ‘ Marcus ‐inverted’ region is observed. The fit with the theory is best, when a nearly solvent‐independent Coulomb term is used in the calculation of the energy balance.