Coherence Maps and Flow of Excitation Energy in the Bacterial Light Harvesting Complex 2.

Abstract

We present and analyze coherence maps [ J. Phys. Chem. B 2022, 126, 9361-9375] to investigate the quantum coherences that are created, sustained, and damped by vibrational modes during the transfer of excitation energy from the B800 (outer) to the B850 (inner) ring of the light harvesting complex 2 (LH2) of purple bacteria with a variety of initial conditions. The reduced density matrix of the 24-pigment complex, where the ground and excited electronic states of each bacteriochlorophyll are explicitly coupled to 50 intramolecular vibrations at room temperature, is obtained from fully quantum-mechanical small matrix path integral (SMatPI) calculations. The coherence maps show a very rapid localization within the outer ring, accompanied by the formation of inter-ring quantum superpositions that evolve to a partial quantum delocalization at equilibrium, and quantify in state-to-state detail the flow of energy within the complex.