Differentiation of correlated fluctuations in site energy on excitation energy transfer in photosynthetic light-harvesting complexes

Abstract

One of the promising approaches to revealing the photosynthetic efficiency of close to one unit is to investigate the quantum regime of excitation energy transfer (EET). The majority of studies, however, have concluded that different pigment molecules contribute equally to EET, rather than differently. We investigate the roles of different site-energies in EET by evaluating the correlated fluctuations of site-energies in two adjacent pigment molecules (namely Site 1 and Site 2), and we attempt to demonstrate different site roles in EET with the j–V characteristics and power via a photosynthetic quantum heat engine (QHE) model rather than an actual photosynthetic protein. The results show that fluctuations at Site 1 (the pigment molecule absorbing solar photons) provide ascending and then descending EET. At Site 2, the EET is reduced through the use of correlated fluctuation increments (the pigment molecule acting as the charge-transfer excited state). Furthermore, when investigating the correlated fluctuations at Site 2, the different gap differences of the output terminal play a positive role in EET, but a sharply decreasing EET process is also achieved with less correlated fluctuations at Site 2 compared to those at Site 1. The findings show that different pigment molecules contribute differently to EET. The significance of this work is that it not only clarifies the roles of different pigment molecules in EET, but it also deepens our understanding of the fundamental physics of EET as it transports through the molecular chain in photosynthetic light-harvesting complexes. Furthermore, the results are appropriate to the EET in organic semiconductors, photovoltaic devices, and quantum networks, when these systems couple to the environment of photons via the vibrational motion of sites in the molecular chain.