Spatially-resolved Fluorescence-detected Two-dimensional Electronic Spectroscopy Probes Varying Electronic Couplings in Photosynthetic Bacteria

Abstract: We present a variation of two-dimensional electronic spectroscopy that is capable of mapping spatially-varying differences in electronic couplings using a correlated map of excitation and detection frequencies, with sensitivity orders of magnitude better than conventional spatially-averaged electronic spectroscopies. The approach performs fluorescence-detection-based fully collinear two-dimensional electronic spectroscopy in a microscope, combining femtosecond time-resolution, sub-micron spatial resolution, and the sensitivity of fluorescence detection. We demonstrate the approach on a mixture of photosynthetic bacteria that are known to exhibit variations in electronic structure with growth conditions. Spatial variations in the constitution of mixed bacterial colonies manifests as spatially-varying peak intensities in the measured two-dimensional contour maps, which exhibit well-resolved electronic couplings between excited electronic states of the bacterial proteins.