Higher-Order Multidimensional and Pump-Probe Spectroscopies

Transient absorption and coherent two-dimensional spectroscopy are widely established methods for the investigation of ultrafast dynamics in quantum systems. Conventionally, they are interpreted in the framework of perturbation theory at the third order of interaction. Here, we discuss the potential of higher-(than-third-)order pump-probe and multidimensional spectroscopy to provide insight into excited multiparticle states and their dynamics. We focus on recent developments from our group. In particular, we demonstrate how phase cycling can be used in fluorescence-detected two-dimensional spectroscopy to isolate higher-order spectra that provide information about highly excited states such as the correlation of multiexciton states. We discuss coherently detected fifth-order 2D spectroscopy and its power to track exciton diffusion. Finally, we show how to extract higher-order signals even from ordinary pump-probe experiments, providing annihilation-free signals at high excitation densities and insight into multiexciton interactions.