Heterogeneous exciton dynamics revealed by two-dimensional optical spectroscopy

We show that optical two-dimensional (2D) spectroscopy can recover ultrafast heterogeneous dynamics of closely spaced delocalized exciton states from a molecular exciton manifold characterized by a single absorption band. The complete experimental third-order nonlinear optical response from room-temperature J-aggregates in liquid phase is reproduced for the first time with self-consistent Frenkel exciton theory combined with modified Redfield theory. We show that exciton relaxation between the exciton states and nuclear-motion-induced exchange-narrowed energy fluctuations of individual delocalized exciton states can be distinguished because these two processes lead to a distinctively different evolution of the absolute 2D spectrum. Our technique also allows recovery of the variation of the exciton relaxation rates as well as the degree of exciton delocalization across the absorption band.