Understanding the mechanisms of efficient and robust energy transfer in light-harvesting systems provides new insights for the optimal design of artificial systems. In this paper, we use the Fenna-Matthews-Olson (FMO) protein complex and phycocyanin 645 (PC 645) to explore the general dependence on physical parameters that help maximize the efficiency and maintain its stability. With the Haken-Strobl model, the maximal energy transfer efficiency (ETE) is achieved under an intermediate optimal value of dephasing rate. To avoid the infinite temperature assumption in the Haken-Strobl model and the failure of the Redfield equation in predicting the Forster rate behavior, we use the generalized Bloch-Redfield (GBR) equation approach to correctly describe dissipative exciton dynamics and find that maximal ETE can be achieved under various physical conditions, including temperature, reorganization energy, and spatial-temporal correlations in noise. We also identify regimes of reorganization energy where the ETE changes monotonically with temperature or spatial correlation and therefore cannot be optimized with respect to these two variables.Photosynthetic processes in plants, bacteria and marine algae provide key insights into designing artificial light harvesting systems that operate efficiently and robustly [1, 2]. The initial stages in the conversion of solar energy into chemical and other useful forms of energy for human consumption can be described by exciton dynamics with trapping and dissipation [3,4]. Recent experimental and computational studies suggest that environmental noise can assist exciton transport and can be optimized for maximal energy transfer efficiency (ETE) [5]- [20]. Quantum entanglement in photosynthetic light-harvesting complexes has also been studied with the consideration of environmental noise [21]. In this paper, using two light-harvesting systems, FMO and PC 645, we examine the optimization of the ETE, with respect to reorganization energy, temperature, and spatial-temporal correlations.This paper closely follows the theoretical formulation presented in a recent review [17] and further examines issues relevant for realistic light-harvesting systems. The review article addresses two questions: basic mechanisms of optimal energy transfer and systematic mapping to kinetic networks. Since environmental noise helps maximize energy transfer efficiency, it stands to reason that light-harvesting systems can be optimized to achieve best performance under a given environment, which leads to the proposal of optimal design. Previous work on simple models [10,17] and FMO [13]-[16] use the Haken-Strobl model, an infinite temperature model, and therefore report optimization a function of single parameter, the pure dephasing rate.It remains an open question if the ETE can be optimized as a function of temperature, reorganization energy, bath correlation time, and spatial correlation. In this paper, we will further examine the idea of noise-enhanced optimal energy transfer with explicit considerations of d...

The most recent crystal structure of the Fenna-Matthews-Olson (FMO) protein complex indicates that each subunit contains an additional eighth chromophore. It has been proposed that this extra site functions as a link between the chlorosome antenna complex and the remaining seven chromophores in FMO [Schmidt am Busch et al, J. Phys. Chem. Lett., 2, 93 (2011)]. Here, we investigate the implications of this scenario through numerical calculations with the generalized Bloch-Redfield (GBR) equation and the non-interacting blip approximation (NIBA). Three key insights into the population dynamics and energy transfer efficiency in FMO are provided. First, it is shown that the oscillations that are often observed in the population relaxation of the dimer composed of sites one and two may be completely suppressed in the eight site model. The presence of the coherent oscillations is shown to depend upon the particular initial preparation of the dimer state. Secondly it is demonstrated that while the presence of the eighth chromophore does not cause a dramatic change in the energy transfer efficiency, it does however lead to a dominant energy transfer pathway which can be characterized by an effective three site system arranged in an equally-spaced downhill configuration. Such a configuration leads to an optimal value of the site energy of the eighth chromophore which is shown to be near to its suggested value. Finally we confirm that the energy transfer process in the eight site FMO complex remains efficient and robust. The optimal values of the bath parameters are computed and shown to be closer to the experimentally fitted values than those calculated previously for the seven site system.

Following the calculation of optimal energy transfer in thermal environment in our first paper (Wu et al., New J. Phys., 2010, 12, 105012), full quantum dynamics and leading-order 'classical' hopping kinetics are compared in the seven-site Fenna-Matthews-Olson (FMO) protein complex.The difference between these two dynamic descriptions is due to higher-order quantum corrections.Two thermal bath models, classical white noise (the Haken-Strobl-Reineker model) and quantum Debye model, are considered. In the seven-site FMO model, we observe that higher-order corrections lead to negligible changes in the trapping time or in energy transfer efficiency around the optimal and physiological conditions (2% in the HSR model and 0.1% in the quantum Debye model for the initial site at BChl 1). However, using the concept of integrated flux, we can identify The eight-site FMO model yields similar trapping time and network structure as the seven-site FMO model but leads to a more disperse distribution of energy transfer pathways.2