Frequency-Dependent Vibronic Effects in Steady State Energy Transport.

The interplay between electronic and intramolecular high-frequency vibrational degrees of freedom is ubiquitous in natural light-harvesting systems. Recent studies have indicated that an intramolecular vibrational donor-acceptor frequency difference can enhance energy transport. Here, we analyze the extent to which different intramolecular donor-acceptor vibrational frequencies affect excitation energy transport in the natural nonequilibrium steady state configuration. Comments are included on the less physical equilibrium case for comparison with the literature. It is found that for constant Huang-Rhys factors, whereas the acceptor population increases in the equilibrium case when the intramolecular vibrational frequency of the acceptor exceeds that of the donor, this increase is negligible for the nonequilibrium steady state. Therefore, these changes in acceptor population do not significantly enhance energy transport in the nonequilibrium steady state for the natural scenario of incoherent light excitation with biologically relevant parameters of typical photosynthetic complexes. Insight about a potential mechanism to optimize energy transfer in the nonequilibrium steady state based on increasing the harvesting time at the reaction center is analyzed.