Synthetic Control of Exciton Dynamics in Bioinspired Cofacial Porphyrin Dimers
Partha Pratim Roy, Sohang Kundu, Jesús Valdiviezo, George Bullard, J. T. FLETCHER, Rui Liu, Shiun-Jr Yang, Peng Zhang, David N. Beratan, Michael J. Therien, Nancy Makri, Graham R. Fleming
Abstract
. Theoretical studies indicate how the interchromophore interactions in these structures, and their system-bath couplings, influence excitonic delocalization and vibronic coherence-enabled rapid exciton transport dynamics. Real-time path integral calculations reproduce the exciton transfer kinetics observed experimentally and find that the linking-modulated exciton delocalization strongly enhances the contribution of vibronic coherences to the exciton transfer mechanism, and that this coherence accelerates the exciton transfer dynamics. These benchmark molecular design, 2DES, and theoretical studies provide a foundation for directed explorations of nonclassical effects on exciton dynamics in multiporphyrin assemblies.