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Intersystem Crossing as a Key Component of the Nonadiabatic Relaxation Dynamics of Bithiophene and Terthiophene

  • Thomas Schnappinger
    Thomas Schnappinger
    Department of Chemistry, Ludwig-Maximilians-Universität München, D-81377 München, Germany
  • Marco Marazzi
    Marco Marazzi
    Departamento de Química, Centro de Investigación en Síntesis Química (CISQ), Universidad de La Rioja, 26006 Logroño, Spain
    Université de Lorraine and CNRS, LPCT UMR 7019, F-54000 Nancy, France
  • Sebastian Mai
    Sebastian Mai
    Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, 1090 Vienna, Austria
  • Antonio Monari
    Antonio Monari
    Université de Lorraine and CNRS, LPCT UMR 7019, F-54000 Nancy, France
  • Leticia González
    Leticia González
    Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, 1090 Vienna, Austria
  • , and 
  • Regina de Vivie-Riedle*
    Regina de Vivie-Riedle
    Department of Chemistry, Ludwig-Maximilians-Universität München, D-81377 München, Germany
    *E-mail: [email protected]
Cite this: J. Chem. Theory Comput. 2018, 14, 9, 4530–4540
Publication Date (Web):August 9, 2018
https://doi.org/10.1021/acs.jctc.8b00492
Copyright © 2018 American Chemical Society

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    Abstract

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    We present a nonadiabatic dynamics study concerning the subpicosecond relaxation of excited states in dimeric and trimeric thiophene chains. The influence of the triplet states in the overall process is, for the first time, taken into account by explicitly including spin–orbit couplings and hence allowing intersystem crossing phenomena. We observe the fundamental role of the triplet state manifold in driving the full relaxation process. In particular we evidence the effect of both, inter-ring rotation and ring-opening, in the process, as compared to the monomer, where the ring-opening process appears as the dominant one. In addition, the evolution of the open structures allows for trans to cis isomerization in the dimer and trimer. The overall relaxation process slows down with chain elongation. The complex decay mechanism characterized by the presence of different competing channels, due to the presence of a quasi degenerate manifold, is explained allowing the rationalization of oligothiophenes photophysics.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jctc.8b00492.

    • Validation of the static quantum chemical calculations and comparison with the reference values, time series of some relevant geometrical coordinates up to the ps time scale and distribution of the hops between the states, coordinates of the optimized geometries of the relevant critical points, evolution of the average population of the states and of the hops between states obtained from the full set of trajectories (PDF)

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