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  • Keith Hughes
  • Irene Burghardt
    Goethe University, Frankfurt, Germany
  • Popp Wjatscheslaw
    Goethe University, Frankfurt, Germany
  • Matthias Polkehn
    Goethe University, Frankfurt, Germany
  • Rocco Martinazzo
    Department of Environmental Science and Policy, Università degli Studi di Milano, Milano, Italy.
A reduced-dimensional effective-mode representation is developed in order to efficiently describe excited-state dynamics of multichromophoric donor-acceptor aggregates within a linear vibronic coupling model. Specifically, we consider systems where vibrational modes pertaining to a given molecular fragment couple both to local excitations of Frenkel type and delocalized states of charge transfer exciton type. A hierarchical chain representation is constructed which is suitable to describe correlated fluctuations, leading to a set of correlated spectral densities. An application is shown for a first-principles parameterized model of an oligothiophene H-type aggregate whose properties are modified due to the presence of charge transfer excitons. Within a pentamer model comprising 13 electronic states and 195 normal modes, good convergence of the effective-mode representation of the spectral densities is achieved at the eighth order of the hierarchy with 104 modes, and a qualitatively correct picture is obtained at the sixth order with 78 modes.
Original languageEnglish
Article number244114
JournalJournal of Chemical Physics
Issue number24
Early online date27 Jun 2019
Publication statusPublished - 28 Jun 2019

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