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In recent years, action-detected ultrafast spectroscopies have gained popularity offering distinct advantages over their coherently-detected counterparts, such as spatially-resolved and operando measurements with high sensitivity. However, there are also fundamental limitations connected to the process of signal generation in action-detected experiments. Here we perform fluorescence- detected two-dimensional electronic spectroscopy (F-2DES) of the light-harvesting II (LH2) complex from purple bacteria. We demonstrate that the B800-B850 energy transfer process in LH2 is weak but observable in F-2DES, unlike in coherently-detected 2DES where the energy transfer is visible with 100% contrast. We explain the weak signatures using a disordered excitonic model that accounts for experimental conditions. We further derive a general formula for the presence of excited-state signals in multichromophoric aggregates, dependent on the aggregate geometry, size, excitonic coupling and disorder. We find that the prominence of excited-state dynamics in action- detected spectroscopy offers a unique probe of excitonic delocalization in multichromophoric systems.more » « less
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Rolczynski, Brian S.; Yeh, Shu-Hao; Navotnaya, Polina; Lloyd, Lawson T.; Ginzburg, Alan R.; Zheng, Haibin; Allodi, Marco A.; Otto, John P.; Ashraf, Khuram; Gardiner, Alastair T.; et al (, The Journal of Physical Chemistry B)null (Ed.)
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