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Entropic effects in excited state CT reactions

Rettig, W.
Published in Chemical Physics Letters. 2009, vol. 469, no. 1, p. 115-120
Abstract The kinetics of the dual fluorescence of several derivatives of dimethylaminobenzonitrile (DMABN) has been compared using fs-fluorescence upconversion experiments. Variation of the size and twist angle of the donor (dialkylamino group) suggest a large amplitude solvent-viscosity controlled diffusional twisting motion towards larger twist angles as the rate limiting step. Large rate differences were observed for an ester group as acceptor. Temperature dependent studies indicate that these differences are not connected with different activation barriers but with changes in the Arrhenius preexponential factor. It is argued that conical intersections along the reaction path can bring about these entropy changes.
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Research group Groupe Vauthey
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PIGLIUCCI, Anatolio, VAUTHEY, Eric, RETTIG, W. Entropic effects in excited state CT reactions. In: Chemical Physics Letters, 2009, vol. 469, n° 1, p. 115-120. https://archive-ouverte.unige.ch/unige:3557

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Deposited on : 2009-10-02

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