Localization length and intraband scattering of excitons in linear aggregates Original Research Article

A theoretical model to describe the intraband scattering of excitons in linear aggregates of finite size which exhibit strong intermolecular interactions is presented. From the calculation of the aggregate eigenstates, the localization length of excitons is evaluated for various configurations featuring physical situations like trapping, edge effects, inclusion of diagonal and/or orientational disorders. The intraband scattering is studied by considering the exciton–phonon stochastic coupling induced by the thermal bath. This coupling creates local dynamical fluctuations in the site energies which are characterized by their amplitude (Δ) and their correlation time (τc). Expressions of scattering rates are provided and used in a Pauli master equation to calculate the time dependence of the eigenstates populations after initial excitation of the quasi exciton-band. It is shown that the time evolution of the lowest state population as well as the Stokes shift strongly depend on τc. Comparison of the theoretical results to time-resolved experiments performed on triaryl pyrylium salts allows us to interpret the observed Stokes shift and to derive an average value of the exciton–phonon correlation time.