Cooperation between Excitation Energy Transfer and Antisynchronously Coupled Vibrations

Abstract

The effects of the environment in energy transfer systems have been continuously studied for decades. Here, we investigate how the energy transfer and the emergence of vibrational correlations cooperate with each other based on simulations with a few numerically approximate mixed quantum classical (MQC) methods. By adopting a two-state system with locally coupled underdamped vibrations that are resonant with the electronic energy gap, we observe prominent energy dissipations from the electronic system to the vibrations, rehighlighting the role of underdamped vibrations as a temporal electronic energy buffer. More importantly, this energy dissipation generates specific phase relations between the two vibrations. Namely, the vibrations become anticorrelated right after the initiation of the energy transfer but then synchronized as the transfer completes. These phase relations are interpreted as a selective activation of an anticorrelated motion of the vibrations and a subsequent deactivation by thermal energy redistribution. Furthermore, we show that a single vibration simultaneously coupled to the two electronic states with opposite phases induces a completely equivalent energy transfer dynamics as the two localized vibrations. Finally, we discuss how the vibrational energy dissipation dynamics is affected by the adopted MQC approaches and warn about the increased subtlety toward properly treating dissipation effects over having reliable population dynamics.