Environmental coupling and population dynamics in the PE545 light-harvesting complex

Long-lived quantum coherences have been shown experimentally in the Fenna–Matthews–Olson (FMO) complex of green sulfur bacteria as well as in the phycoerythrin 545 (PE545) photosynthetic antenna system of marine algae. A combination of classical molecular dynamics simulations, quantum chemistry and quantum dynamical calculations is employed to determine the excitation transfer dynamics in PE545. One key property of the light-harvesting system concerning the excitation transfer and dephasing phenomena is the spectral density. This quantity is determined from time series of the vertical excitation energies of the aggregate. In the present study we focus on the quantum dynamical simulations using the earlier QM/MM calculations as input. Employing an ensemble-averaged classical path-based wave packet dynamics, the excitation transfer dynamics between the different bilins in the PE545 complex is determined and analyzed. Furthermore, the nature of the environmental fluctuations determining the transfer dynamics is discussed. - Highlights: • Modeling of excitation energy transfer in the light-harvesting system PE545. • Combination of molecular dynamics simulations, quantum chemistry and quantum dynamics. • Spectral densities for bilins in the PE545 complex.