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Viscosity Effect on the Rate of Back Electron-Transfer within a Short-Lived Exciplex

Contributeurs/tricesVauthey, Ericorcid; Phillips, David
Publié dansChemical physics, vol. 147, no. 2-3, p. 421-430
Date de publication1990
Résumé

A study of viscosity and temperature effects on the rate of back electron transfer (BET) within an exciplex (9,10-dicyanoanthracene/N,N-dimethylaniline) with a strong charge transfer character in six non-polar solvents is reported. The extent of charge transfer has been estimated from the solvatochromic and thermochromic shifts of the fluorescence. Conformational changes are a prerequisite to the BET. In non-viscous solvents, where they are much faster than the ET step itself, the observed rate can be explained within the theory of non-adiabatic ET reactions, while in more viscous solvents, a time-dependent electronic coupling constant V has been introduced. In decalin and butylbenzene, a transition from a "solvent independent" to a "solvent controlled" non-adiabatic regime is observed.

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Citation (format ISO)
VAUTHEY, Eric, PHILLIPS, David. Viscosity Effect on the Rate of Back Electron-Transfer within a Short-Lived Exciplex. In: Chemical physics, 1990, vol. 147, n° 2-3, p. 421–430. doi: 10.1016/0301-0104(90)85056-3
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ISSN du journal0301-0104
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Création21.09.2009 16:19:50
Première validation21.09.2009 16:19:50
Heure de mise à jour14.03.2023 15:13:22
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