Signatures of exciton dynamics and interaction in coherently and fluorescence-detected four- and six-wave-mixing two-dimensional electronic spectroscopy

Two-dimensional electronic spectroscopy (2DES) can be realized in increasing nonlinear orders of interaction with the electric field, bringing new information about single- and multi-particle properties and dynamics. Furthermore, signals can be detected both coherently (C-2DES) and by fluorescence (F-2DES), with fundamental and practical differences. We directly compare the simultaneous measurements of four- and six-wave mixing C-2DES and F-2DES on an excitonic heterodimer of squaraine molecules. Spectral features are described in increasing orders of nonlinearity by an explicit excitonic model. We demonstrate that the four-wave-mixing spectra are sensitive to one-exciton energies, their delocalization and dynamics, while the six-wave-mixing spectra include information on bi-exciton and higher excited states including the state energies, electronic coupling, and exciton–exciton annihilation. We focus on the possibility to extract the dynamics arising from exciton–exciton interaction directly from the six-wave-mixing spectra. To this end, in analogy to previously demonstrated fifth-order coherently detected exciton–exciton-interaction 2DES (EEI2D spectroscopy), we introduce a sixth-order fluorescence-detected EEI2D spectroscopy variant.