Fluorescence-Detected Two-Quantum Photon Echoes via Cogwheel Phase Cycling

Two-dimensional (2D) electronic spectroscopy can separate homogeneous and inhomogeneous broadening. While established methods usually probe a photon-echo signal, i.e., a third-order response, to access the homogeneous line width of singly excited states, the homogeneous line width of doubly excited states remained spectroscopically inaccessible. Here we demonstrate the acquisition of two-quantum (2Q) photon echoes using fluorescence-detected 2D spectroscopy. In these eighth-order signals, 2Q coherences are rephased with themselves, leading to line-narrowed 2Q-2Q 2D spectra. By using cogwheel phase cycling, adapted from nuclear magnetic resonance spectroscopy, we isolate the 2Q-2Q 2D spectra of a squaraine dimer and a squaraine polymer and verify the same selectivity of cogwheel phase cycling compared to traditional "nested" phase cycling. The observed difference, between the two systems, in the homogeneous line width of the biexciton can be rationalized as a signature of the interplay of exciton-exciton annihilation, exciton diffusion, and exciton delocalization.