American Chemical Society
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Quantum Ratcheted Photophysics in Energy Transport

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journal contribution
posted on 2020-09-18, 21:47 authored by Pallavi Bhattacharyya, Graham R. Fleming
In this paper, we explore the scope of vibrations as quantum ratchets that serve as nonthermal routes to achieving population transport in systems where excitation transport between molecules is otherwise energetically unfavorable. In addition to their role as channels of transport, we investigate the effect of resonance of the vibrations, which are described by Huang–Rhys mixing, with excitonic energy gaps, which leads to strongly mixed vibronic excitons. Finally, we explore the interplay of resonance and Huang–Rhys mixing with electronic coupling between the molecules, in the presence of a dissipative bath, in optimizing transport in such systems. We find that while resonance is desirable, a moderate electronic coupling has a stronger positive effect in contrast to a large electronic coupling, which results in delocalized excitations across molecules and hampers unidirectional transport. We also report a special resonance regime that is able to circumvent the transport problems arising from large electronic couplings.