Two-dimensional spectroscopy of molecular excitons in a model dimer system

The physics of molecular excitons has been the subject of many recent studies using electronic two-dimensional photon-echo spectroscopy (2DPE), particularly in the context of light harvesting in photosynthesis. Since the spectra for multichromophoric aggregates are congested, particularly so at room temperature, we present a study of a model dimer comprised of identical chromophores with a well defined electronic coupling strength, to provide clear signatures for coherences between vibronic excitons in 2D spectra. We begin by describing the design of a broadband passively phase-stabilized interferometer for collection of 2D spectra, which also allows for the investigation of state preparation in 2D spectroscopy by using shaped excitation pulses. In experiments on the model dimer we observe strong oscillating off-diagonal features in the 2D spectra which are present only before the onset of dephasing, which occurs in less than 100 fs due to strong system-bath coupling. This is in contrast with the parent dye, where low amplitude oscillations associated with Raman active vibrations persist for several ps following excitation. The results of this comparative study indicate that the signals observed earlier in photosynthetic proteins likely reflect vibrational motion in isolated pigments, and not delocalized quantum coherence. While long-lived vibrational coherences are of questionable biological relevance at face value, we conclude with a discussion on initial findings using coherently controlled 2D spectroscopy, where we observe long-lived signatures associated to vibronic coherences at room temperature. These results point to new directions of study using multidimensional spectroscopy to unravel the role of coherence in excitation energy transfer in molecular aggregates in an experimentally direct fashion.