Coherence and Efficient Energy Transfer in Molecular Wires: Insights from Surface Hopping Simulations

Understanding the dynamics of electronic energy transfer through a molecular wire is essential to understand the working of natural processes like photosynthesis. We investigate simpler 2 and 3-site model Hamiltonians in this work to understand the importance of coherence to efficient energy transfer. We compare the results of surface hopping simulation with that of numerically exact results and rate theories. Different parameters are analyzed, motivated by a photosynthetic molecular wire - the FMO complex. A comparison of results from different theories shows that coherence can play an important role towards efficient energy transfer for certain parameters. When these coherences are important, even small couplings (of the order of 5 cm(-1)) in the Hamiltonian can significantly affect rates. Surface hopping simulations capture all the results correctly qualitatively. Rate theories, on the other hand, can differ significantly from numerically exact results when coherences become important. The results of this work should provide design guidelines for efficient energy transfer in molecular wires.