Frequency-Dependent Vibronic Effects in Steady State Energy Transport

Abstract: 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 equilibrium (coherent light excitation) and the more natural nonequilibrium steady state (incoherent light excitation) configurations. It is found that if the Huang-Rhys factors remain constant, the acceptor population increases when the intramolecular vibrational frequency of the acceptor exceeds that of the donor. The increase in the acceptor population due to the vibrational frequency difference is higher for higher values of the Huang-Rhys factors or the vibronic coupling strengths. However, the nonequilibrium steady state results show that the vibrational donor-acceptor frequency difference does not significantly enhance energy transport in the natural scenario of incoherent light excitation and under biologically relevant parameters. Insight about a potential mechanism to optimize energy transfer in the NESS based on increasing the harvesting time at the reaction center is analyzed.