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Temperature Dependence of Ultra‐Exothermic Charge Recombinations
Author(s) -
Serpa Carlos,
Gomes Paulo J. S.,
Arnaut Luis G.,
de Melo J. Seixas,
Formosinho Sebastião J.
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200600467
Subject(s) - chemistry , ion , hydrocarbon , charge (physics) , solvent , electron , electron acceptor , exothermic reaction , recombination , electron donor , photochemistry , organic chemistry , biochemistry , physics , quantum mechanics , gene , catalysis
We measured the temperature dependence (from +32 to −50 °C) of charge‐recombination rates between contact radical ion pairs in isopropyl ether. In the systems selected for this study, aromatic hydrocarbon cations are the electron acceptors and the fumaronitrile anion is the electron donor. Nearly quantitative electron transfers occur at all temperatures. The charge recombinations have excess exothermicities of −60 kcal mol −1 and exhibit a very weak temperature dependence. Our observations emphasize the absence of solvent effects and the relevance of nuclear tunneling in charge recombinations.