Theoretical Investigation on Triplet Excitation Energy Transfer in Fluorene Dimer

Abstract

Triplet-triplet energy transfer in fluorene dimer is investigated by combining rate theories with electronic structure calculations. The two key parameters for the control of energy transfer, electronic coupling and reorganization energy, are calculated based on the diabatic states constructed by the constrained density functional theory. The fluctuation of the electronic coupling is further revealed by molecular dynamics simulation. Succeedingly, the diagonal and off-diagonal fluctuations of the Hamiltonian are mapped from the correlation functions of those parameters, and the rate is then estimated both from the perturbation theory and wavepacket diffusion method. The results manifest that both the static and dynamic fluctuations enhance the rate significantly, but the rate from the dynamic fluctuation is smaller than that from the static fluctuation.