Vibronic coupling models for donor-acceptor aggregates using an effective-mode scheme: Application to mixed Frenkel and charge-transfer excitons in oligothiophene aggregates
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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 language | English |
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Article number | 244114 |
Journal | Journal of Chemical Physics |
Volume | 150 |
Issue number | 24 |
Early online date | 27 Jun 2019 |
DOIs | |
Publication status | Published - 28 Jun 2019 |
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