<br/>Fluorescence-Detected Two-Dimensional Electronic Spectroscopy can be used for microscopy and, thus, allow for imaging of ultrafast phenomena. Here, we present a theory for modeling fluorescence-detected two-dimensional electronic spectroscopy of multichromophoric systems. We present a test of the theory by comparison of the predicted spectra of the light-harvesting complex LH2 with experimental data. A qualitative explanation of the strong cross-peaks as compared to conventional two-dimensional electronic spectra is given. The strong cross-peaks are attributed to the clean ground-state signal that is revealed when the annihilation of exciton pairs created on the same LH2 complex cancels oppositely signed signals from the doubly excited state. This annihilation process occurs much faster than the nonradiative relaxation. Furthermore, we explain the lineshape difference by slow dynamics, exciton delocalization within the bands, and intraband exciton−exciton annihilation. The use of time-resolved fluorescence-detected two-dimensional spectroscopy to study state-resolved exciton−exciton annihilation is, therefore proposed.

Fluorescence-detected two-dimensional electronic spectroscopy of multichromophoric systems

2019 Fall National Meeting

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