Observation of Electronic Excitation Transfer through Light Harvesting Complex II Using Two-dimensional Electronic-vibrational Spectroscopy.

Light Harvesting Complex II (LHCII) serves a central role in light harvesting for oxygenic photosynthesis, and is arguably the most important photosynthetic antenna complex. In this work, we present two-dimensional electronic-vibrational (2DEV) spectra of LHCII isolated from spinach, demonstrating the possibility of using this technique to track the transfer of electronic excitation energy between specific pigments within the complex. We assign the spectral bands via comparison with the 2DEV spectra of the isolated chromophores, chlorophyll a and b, and present evidence that excitation energy between the pigments of the complex are observed in these spectra. Finally, we analyze the essential components of the 2DEV spectra using singular value decomposition, which makes it possible to reveal the relaxation pathways within this complex.