Pulling the Levers of Photophysics: How Structure Controls the Rate of Energy Dissipation

Authors

  • Thomas S. Kuhlman,

    1. Department of Chemistry, Technical University of Denmark, Kemitorvet 207, 2800 Kgs. Lyngby (Denmark)
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  • Prof. Michael Pittelkow,

    1. Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 København Ø (Denmark)
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  • Prof. Theis I. Sølling,

    Corresponding author
    1. Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 København Ø (Denmark)
    • Theis I. Sølling, Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 København Ø (Denmark)===

      Klaus B. Møller, Department of Chemistry, Technical University of Denmark, Kemitorvet 207, 2800 Kgs. Lyngby (Denmark)===

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  • Prof. Klaus B. Møller

    Corresponding author
    1. Department of Chemistry, Technical University of Denmark, Kemitorvet 207, 2800 Kgs. Lyngby (Denmark)
    • Theis I. Sølling, Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 København Ø (Denmark)===

      Klaus B. Møller, Department of Chemistry, Technical University of Denmark, Kemitorvet 207, 2800 Kgs. Lyngby (Denmark)===

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  • T.I.S. acknowledges the Villum foundation and M.P. acknowledges the Danish Council for Independent Research/Natural Sciences and the Lundbeck Foundation for financial support. The Danish Center for Scientific Computing (DCSC) is acknowledged for computational resources.

Abstract

original image

Internal conversion: The energy difference between the Franck–Condon and equilibrium geometries and the vibrational frequency of one or a few modes determine the relative importance of adiabatic and nonadiabatic dynamics and thus the rate of electronic energy dissipation (see picture). In the cycloketones, variations in these quantities lead to a difference in the timescale for the S2→S1 transition.

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