Abstract
Two-dimensional (2D) ultrafast spectroscopy has been used widely in the infrared (IR) and increasingly in the visible to probe excitonic couplings and observe dynamics, but the off-diagonal spectral signatures of coupling are often obscured by broad diagonal peaks. The use of polarized pulse sequences to elucidate cross-peaks in 2D spectra has been demonstrated in the IR for vibrational transitions.
Here we develop 2D electronic spectroscopy using cross-peak-specific pulse polarization conditions in an investigation of the Fenna-Matthews-Olson light harvesting complex from green photosynthetic bacteria. Our measurements successfully highlight off-diagonal features of the 2D spectra and, in combination with an analysis based on the signs of features arising from particular energy level pathways and theoretical simulation, we characterize the dominant response pathways responsible for the spectral features.