Vibronic phenomena and exciton-vibrational interference in two-dimensional spectra of molecular aggregates

Abstract

A general theory of electronic excitations in aggregates of molecules coupled to intramolecular vibrations and the harmonic environment is developed for simulation of the third-order nonlinear spectroscopy signals. The model is applied in studies of the time-resolved two-dimensional coherent spectra of four characteristic model systems: weakly / strongly vibronically coupled molecular dimers coupled to high / low frequency intramolecular vibrations. The results allow us to classify the typical spectroscopic features as well as to define the limiting cases, when the long-lived quantum coherences are present due to vibrational lifetime borrowing, when the complete exciton-vibronic mixing occurs and when separation of excitonic and vibrational coherences is proper.

16 pages, 7 figures

References in corpus (7)

• The fundamental role of quantized vibrations in coherent light harvesting by cryptophyte algae
• Long-Lived Electronic Coherence in Dissipative Exciton-Dynamics of Light-Harvesting Complexes
• Distinctive character of electronic and vibrational coherences in disordered molecular aggregates
• Exploiting structured environments for efficient energy transfer: The phonon antenna mechanism
• Molecular vibrations-induced quantum beats in two-dimensional electronic spectroscopy
• Vibrational wave packet induced oscillations in two-dimensional electronic spectra. I. Experiments
• Vibrational wave packet induced oscillations in two-dimensional electronic spectra. II. Theory

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