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Electronic Bond-to-Bond Fluxes in Pericyclic Reactions: Synchronous or Asynchronous?

Authors

  • Timm Bredtmann,

    Corresponding author
    1. Institut für Chemie und Biochemie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin (Germany)
    • Institut für Chemie und Biochemie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin (Germany)
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  • Prof. Dr. Jörn Manz

    Corresponding author
    1. Institut für Chemie und Biochemie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin (Germany)
    • Institut für Chemie und Biochemie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin (Germany)
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  • We would like to thank Professors W. T. Borden, D. J. Diestler, K. N. Houk, D. A. Hrovat, H. Kono, B. Paulus, H. Quast, K. Takatsuka, W. Thiel, and R. V. Williams for helpful discussions and encouragement, and Prof. H.-C. Hege and F. Marquardt for introducing us to the program Amira for visualization. Financial support by Deutsche Forschungsgemeinschaft (project Ma 515/25-1) and Fonds der Chemischen Industrie is also gratefully acknowledged.

Abstract

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One at a time or all at once? Electronic fluxes during a pericyclic reaction in the electronic ground state—exemplified for the degenerate Cope rearrangement of semibullvalene—may proceed either synchronously or asynchronously. Quantum simulations show that the mechanism is determined by the preparation of the reactants, for example, synchronous at cryogenic temperatures (tunneling) but asynchronous when induced by selective laser pulses (with energy over the barrier).

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