Two-Color Nonlinear Spectroscopy for the Rapid Acquisition of Coherent Dynamics

There has been considerable recent interest in the observation of coherent dynamics in photosynthetic systems by 2D electronic spectroscopy (2DES). In particular, coherences that persist during the "waiting time" in a 2DES experiment have been attributed to electronic, vibrational, and vibronic origins in various systems. The typical method for characterizing these coherent dynamics requires the acquisition of 2DES spectra as a function of waiting time, essentially a 3DES measurement. Such experiments require lengthy data acquisition times that degrade the signal-to-noise of the recorded coherent dynamics. We present a rapid and high signal-to-noise pulse-shaping-based approach for the characterization of coherent dynamics. Using chlorophyll a, we demonstrate that this method retains much of the information content of a 3DES measurement and provides insight into the physical origin of the coherent dynamics, distinguishing between ground and excited state coherences. It also enables high resolution determination of ground and excited state frequencies.