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.