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

Phillips, David
Published in Chemical Physics. 1990, vol. 147, no. 2-3, p. 421-430
Abstract 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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Research group Groupe Vauthey
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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 https://archive-ouverte.unige.ch/unige:3060

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Deposited on : 2009-09-21

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