Characterization of the coherent dynamics of bacteriochlorophyll a in solution

Disclosing the physical origin of quantum beatings in the early dynamics of biological light-harvesting pigment-protein complexes is one of the major challenges in the ultrafast spectroscopy community. 2D electronic spectroscopy (2DES) is a powerful tool for this purpose, but the complexity of the beating behavior in multi-chromophoric systems complicates the interpretation. For this reason, the availability of control datasets providing a full characterization of the response of isolated chromophores is highly desirable to untangle the features of intermolecular interactions from the properties of individual pigments. Here, a thorough 2DES characterization of the frequencies and dephasing times of intramolecular vibrational coherences of bacteriochlorophyll a in solution is provided. Several beating modes in the ground and excited state have been found and their dephasing times have been determined. The obtained results represent an essential interpretation key of the beating dynamics of pigment-protein complexes binding bacteriochlorophyll a.