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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
Volume150
Issue number24
Early online date27 Jun 2019
DOIs
Publication statusPublished - 28 Jun 2019

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