Photosystem I (PSI) is one of the most efficient natural photosynthetic complexes and serves as a structural prototype for understanding excitation energy transfer (EET) and designing artificial light-harvesting systems. Here, we construct a multilayer elliptical-conical quantum network inspired by PSI to investigate how antenna architecture affects EET. Excitation dynamics are simulated using the quantum jump approach combined with coherent modified Redfield theory (QJA-CMRT). The transfer efficiency exhibits a pronounced nonmonotonic dependence on pigment density, reaching a maximum of 0.86 at x=6 in the five-layer network. The optimal configuration contains 91 pigments, close to the number of core antenna pigments in natural PSI. Our combined density-of-states and kinetic analyses reveal that this nonmonotonic dependence originates from a trade-off: at low pigment densities, enhanced band overlap promotes energy transfer, whereas at high densities, excessive exciton delocalization compromises funnel directionality and reduces efficiency; the optimal configuration is consequently achieved at x=6. These findings provide insights into PSI antenna organization and offer guidelines for designing efficient artificial light-harvesting systems.
Photosystem I (PSI) is one of the most efficient natural photosynthetic complexes and serves as a structural prototype for understanding excitation energy transfer (EET) and designing artificial light-harvesting systems. Here, we construct a multilayer elliptical-conical quantum network inspired by PSI to investigate how antenna architecture affects EET. Excitation dynamics are simulated using the quantum jump approach combined with coherent modified Redfield theory (QJA-CMRT). The transfer efficiency exhibits a pronounced nonmonotonic dependence on pigment density, reaching a maximum of 0.86 at x=6 in the five-layer network. The optimal configuration contains 91 pigments, close to the number of core antenna pigments in natural PSI. Our combined density-of-states and kinetic analyses reveal that this nonmonotonic dependence originates from a trade-off: at low pigment densities, enhanced band overlap promotes energy transfer, whereas at high densities, excessive exciton delocalization compromises funnel directionality and reduces efficiency; the optimal configuration is consequently achieved at x=6. These findings provide insights into PSI antenna organization and offer guidelines for designing efficient artificial light-harvesting systems.
Photosynthetic antenna complexes achieve high quantum efficiency through exciton transport in coupled pigment networks. Conventional Frenkel-exciton models treat each chromophore as a structureless site and neglect internal electronic degrees of freedom that can influence coherence and delocalization. Here we develop an extended excitonic network model that preserves the pigment-pigment coupling topology while introducing tunable intrachromophoric electronic mixing within the single-excitation manifold. Using a Lindblad open-quantum-system framework, we quantify coherence, delocalization, and trapping efficiency across parameter space. We show that intrachromophoric mixing plays a time-dependent role: enhanced mixing on the antenna side promotes short-time coherent delocalization and improves excitation injection, whereas excessive mixing near the trapping site induces persistent delocalization and suppresses transfer efficiency. Simulated two-dimensional electronic spectra reveal enhanced cross peaks and systematic blue shifts, providing spectroscopic signatures of coherence-modulated transport. These results establish a microscopic connection between internal electronic structure and quantum transport performance in excitonic networks.
We investigate coherent and incoherent excitation transfer in a random network with dipole–dipole interactions as a model system describing energy transport, e.g., in photosynthetic light-harvesting complexes or gases of cold Rydberg atoms. For this purpose, we introduce and compare two different measures (the maximum output probability and the average transfer time) for the efficiency of transport from the input to the output site. We especially focus on optimal configurations which maximize the transfer efficiency and the impact of dephasing noise on the transport dynamics. For most configurations of the random network, the transfer efficiency increases when adding noise, giving rise to essentially classical transport. These noise-assisted configurations are, however, systematically less efficient than the optimal configurations. The latter reach their highest efficiency for purely coherent dynamics, i.e. in the absence of noise. 1.
The energy-transfer efficiency of the natural photosynthesis system seems to be perfectly optimized during the evolution for millions of years. However, how to enhance the efficiency in the artificial light-harvesting systems is still unclear. In this paper, we investigate the energy-transfer process in the photosystem I (PSI). When there is no effective coupling between the outer antenna (OA) and the reaction center (RC), the two light-harvesting networks are disconnected and thus the energy transfer is inefficient. In order to repair these disconnected networks, we introduce a bridge with three sites between them. We find that by modulating the level structure of the 3-site bridge to be resonant, the energy transfer via the dark state will be enhanced and even outperform the original PSI. Our discoveries may shed light on the designing mechanism of artificial light-harvesting systems.
Recently, long-lasting quantum effects in a number of photosynthetic complexes, which are pigment-protein molecular aggregates (PPMAs), were experimentally verified. These findings created an interest in trying to connect the known highly efficient excitation energy transfer (EET) in these systems to the existence of quantum effects such as quantum coherence and quantum correlations. It also raised the question of how these sensitive quantum effects can survive in such a macroscopic system. This thesis explores the existence and possible role of quantum effects in the EET in PPMAs. These systems can be modeled as non-Markovian open quantum systems and quantum effects can be investigated and quantified by methods developed in quantum information theory. Firstly, it is found that quantum nonlocal correlations in the EET in the Fenna-Matthews-Olson complex - a PPMA found in nature - are unlikely to exist when the initial excitation occurs in a natural manner. When the initial excitation occurs in an artificial manner by localization of the excitation on one pigment, nonlocal correlations exist on a short time scale. It is further found that in order for nonlocal correlations to be preserved in such a system, the excitation must be trapped on two pigments at the time and these pigments must not interact strongly with other pigments in the complex. Secondly, it is shown that quantum coherence is not in general a resource for efficient EET in model systems consisting of a network of pigments; systems optimized with respect to the amount of coherence do not coincide with systems with optimal EET efficiency between two end-site pigments. Thirdly, it is found that environmental effects and system-environment interactions can be tuned to optimize the EET efficiency in model PPMAs. The features of optimal environments highly depends on the structure of the pigment system and in particular, the relationship between the pigments excitation energies. It is further shown that a non-Markovian dynamics cannot be connected to an increased EET efficiency in these systems.
Recently, the coherent modified Redfield theory (CMRT) has been widely used to simulate the excitation-energy-transfer (EET) processes in photosynthetic systems. However, the numerical simulation of the CMRT is computationally expensive when dealing with large-scale systems, e.g. photosystem I (PSI) and II (PSII). On the other hand, the chemical reaction and fluorescence loss traditionally treated by the non-Hermitian Hamiltonian approach may result in significantly error in a wide range of parameters. To address these issues, we introduce a quantum jump approach (QJA) based on the CMRT to simulate the evolution of photosynthetic complexes including both the chemical reaction and fluorescence loss. The QJA shows higher accuracy and efficiency in simulating the EET processes. The QJA-CMRT approach may provide a powerful tool to design and optimize artificial photosynthetic systems, which benefits future innovation in the field of energy.
Abstract Near-unity energy transfer efficiency has been widely observed in natural photosynthetic complexes. This phenomenon has attracted broad interest from different fields, such as physics, biology, chemistry, and material science, as it may offer valuable insights into efficient solar-energy harvesting. Recently, quantum coherent effects have been discovered in photosynthetic light harvesting, and their potential role on energy transfer has seen the heated debate. Here, we perform an experimental quantum simulation of photosynthetic energy transfer using nuclear magnetic resonance (NMR). We show that an N-chromophore photosynthetic complex, with arbitrary structure and bath spectral density, can be effectively simulated by a system with log2N qubits. The computational cost of simulating such a system with a theoretical tool, like the hierarchical equation of motion, which is exponential in N, can be potentially reduced to requiring a just polynomial number of qubits N using NMR quantum simulation. The benefits of performing such quantum simulation in NMR are even greater when the spectral density is complex, as in natural photosynthetic complexes. These findings may shed light on quantum coherence in energy transfer and help to provide design principles for efficient artificial light harvesting.