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"Ultrafast Femtosecond Charge Transfer: Switching from Adiabatic to Nonadiabatic by Small Structural Changes
Dynamics" S. Lochbrunner, K. Stock, T. Fiebig, E. Pandurski, and E. RiedleFemtochemistry and Femtobiology: Ultrafast Dynamics in Molecular Science, A. Douhal and J. Santamaria, eds. (World Scientific Publishing House, 2002), 328 - 334 Abstract: The intramolecular charge transfer (CT) dynamics of three pyrenyl biphenyl ester isomers have been studied by femtosecond absorption spectroscopy. Two of them show an ultrafast CT and associated relaxation processes whereas the CT of the third one is slower by several orders of magnitude. The differing topology of the acceptor orbitals at the biphenyl ester moieties results in strong changes of the electronic coupling between the locally excited and the CT state. This leads to dynamics on adiabatic potential energy surfaces for the former two compounds and to a weak coupling regime for the latter one. It indicates that the charge flow in molecular systems can be designed in a deterministic manner with minor changes of other system properties by utilizing the topology of the acceptor orbitals. BMO authors (in alphabetic order): Stefan Lochbrunner Eberhard Riedle Kai Stock Order Hardcopy |