Mechanistic insight into internal conversion process within Q-bands of chlorophyll a.

The non-radiative relaxation of the excitation energy from higher energy states to the lowest energy state in chlorophylls is a crucial preliminary step for the process of photosynthesis. Despite the continuous theoretical and experimental efforts to clarify the ultrafast dynamics of this process, it still represents the object of an intense investigation because the ultrafast timescale and the congestion of the involved states makes its characterization particularly challenging. Here we exploit 2D electronic spectroscopy and recently developed data analysis tools to provide more detailed insights into the mechanism of internal conversion within the Q-bands of chlorophyll a. The measurements confirmed the timescale of the overall internal conversion rate (170 fs) and captured the presence of a previously unidentified ultrafast (40 fs) intermediate step, involving vibronic levels of the lowest excited state.