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  • Entropic effects in excited...
    Pigliucci, A.; Vauthey, E.; Rettig, W.

    Chemical physics letters, 02/2009, Letnik: 469, Številka: 1-3
    Journal Article

    The large amplitude motion connected with CT formation in DMABN is controlled by the activation entropy (the Arrhenius prefactor). A possible explanation is a conical intersection necessitating a two-dimensional description of the reaction. 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.