Control of Excitation Energy Transfer in Condensed Phase Molecular Systems by Floquet Engineering

Abstract: Excitation energy transfer (EET) is one of the most important processes in both natural and artificial chemical systems including, for example, photosynthetic complexes and organic solar cells. The EET rate, however, is strongly suppressed when there is a large difference in the excitation energy between the donor and acceptor molecules. Here, we demonstrate both analytically and numerically that the EET rate can be greatly enhanced by periodically modulating the excitation energy difference. The enhancement of EET by using this Floquet engineering, in which the system's Hamiltonian is made periodically time-dependent, turns out to be efficient even in the presence of strong fluctuations and dissipations induced by the coupling with a huge number of dynamic degrees of freedom in the surrounding molecular environments. As an effect of the environment on the Floquet engineering of EET, the optimal driving frequency is found to depend on the relative magnitudes of the system and environment's characteristic time scales with an observed frequency shift when moving from the limit of slow environmental fluctuations (inhomogeneous broadening limit) to that of fast fluctuations (homogeneous broadening limit).