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.