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Perlík, Václav; Sláma, Vladislav; Lincoln, Craig N.; Langhals, Heinz; Riedle, Eberhard; Mančal, Tomáš; Hauer, Jürgen; Šanda, František (8. August 2018): Geometric dependencies of vibronically mediated excitation transfer in rylene dyads. arxiv.org
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We study the excitation transfer in various geometric arrangements of rylene dimers using absorption, fluorescence and transient absorption spectra. Polarization and detection frequency dependencies of transient absorption track the interplay of transfer and vibrational relaxation within the dyads. We have resolved microscopic parametrization of intermolecular coupling between rylenes and reproduced transport data. Dynamical sampling of molecular geometries captures thermal fluctuations for Quantum Chemical estimate ofcouplings for orthogonally arranged dyad, where static estimates vanish and normal mode analysis of fluctuations underestimates them by an order of magnitude. Nonperturbative accounts for the modulation of transport by strongly coupled anharmonic vibrational modes is provided by a vibronic dimer model. Vibronicdynamics is demonstrated to cover both the Förster transport regime of orthogonally arranged dyads and thestrong coupling regime of parallel chromophores and allows us to model signal variations along the detection frequency.