Exciton Dynamics from Strong to Weak Coupling Limit Illustrated on a Series of Squaraine Dimers

We present a joint theoretical and experimental study on the light-induced exciton relaxation dynamics in a series of three squaraine dimers spanning the range from weak to intermediate to strong excitonic coupling strength regime. As revealed by transient-absorption spectroscopy and mixed quantum-classical dynamics simulations that explicitly take into account excitation by the laser pulse, three different types of exciton dynamics could be observed, although the investigated systems exhibit very similar spectral features. While in the strongly coupled system (Frenkel limit), the exciton remains delocalized over both dye monomers, in the system with intermediate coupling, transient localization–delocalization on a femtosecond time scale can be observed. Finally, in the weakly coupled heterodimer (Förster limit), efficient exciton transfer, mediated by transient delocalization that correlates with a strong nonadiabatic coupling, takes place. By delivering the first systematic microscopic study on different regimes of exciton transfer, our findings shed new light on the possible mechanisms of energy transport in organic molecular excitonic materials.