Energy transfer in BChl aggregates

The mechanism of excitation energy transfer in photoexcited bacteriochlorophyll (BChl) aggregates poses intriguing questions, which have important implications for the observed efficiency of photosynthesis. We investigated this process through fully quantum mechanical calculations of exciton-vibration dynamics in chains and rings of BChl a molecules, with parameters characterizing the B850 ring of the LH2 complex of photosynthetic bacteria. The calculations were performed using the modular path integral (MPI) methodology, which allows the exact treatment of 50 intramolecular vibrations on each pigment using parameters obtained from spectroscopic Huang-Rhys factors with computational effort that scales linearly with aggregate length. Our results indicate that the interplay between electronic and vibrational timescales leads to the rapid suppression but not the overdamping of electronic coherence, which facilitates the spreading of excitation energy throughout the aggregate.

For more information, see

Kundu and N. Makri, “Real-time path integral simulation of exciton-vibration dynamics in light harvesting bacteriochlorophyll aggregates”, J. Phys. Chem. Letters 11, 8783-8789 (2020).