Electronic-vibrational resonance damping time-dependent photosynthetic energy transfer acceleration revealed by 2D electronic spectroscopy

The effects of damping time of electronic-vibrational resonance modes on energy transfer in photosynthetic light-harvesting systems are examined. Using the hierarchical equations of motion (HEOM) method, we simulate the linear absorption and two-dimensional electronic spectra (2DES) for a dimer model based on bottleneck sites in the light-harvesting complex of photosystem II. A site-dependent spectral density is incorporated, with only the low-energy site being coupled to the resonance mode. Similar patterns are observed in linear absorption spectra and early time 2DES for various damping times, owing to the weak coupling strength. However, notable differences emerge in the dynamics of the high-energy diagonal and cross-peaks in the 2DES. It is found that the coupling of electronic-vibrational resonance modes accelerates the energy transfer process, with rates being increased as the damping time is extended, but the impact becomes negligible when the damping time exceeds a certain threshold. To evaluate the reliability of the perturbation method, the modified Redfield (MR) method is employed to simulate 2DES under the same conditions. The results from the MR method are aligned with those obtained from the HEOM method, but the MR method predicts faster dynamics.