Photosynthesis powers life on our planet. The basic photosynthetic architecture comprises antenna complexes to harvest solar energy and reaction centers to convert the energy into a stable charge separated state. In oxygenic photosynthesis, the initial charge separation event occurs in the photosystem II reaction center; the only known natural enzyme that uses solar energy to split water. Energy transfer and charge separation in photosynthesis are rapid and have high quantum efficiencies. Recently, nonlinear spectroscopic experiments have suggested that electronic coherence may play a role in energy transfer efficiency in antenna complexes. Here we report the observation of coherence in the photosystem II reaction center by two dimensional electronic spectroscopy. The frequencies of the observed coherences match exciton difference frequencies and/or known vibrational modes of the photosystem II reaction center. These observations raise questions about the possible role of electronic and/or vibrational coherence in the fundamental charge separation process in oxygenic photosynthesis.
The photosystem II reaction centre is the photosynthetic complex responsible for oxygen production on Earth. Its water splitting function is particularly favoured by the formation of a stable charge separated state via a pathway that starts at an accessory chlorophyll. Here we envision a photovoltaic device that places one of these complexes between electrodes and investigate how the mean current and its fluctuations depend on the microscopic interactions underlying charge separation in the pathway considered. Our results indicate that coupling to well resolved vibrational modes does not neces…
The photosystem II reaction center (PSII-RC) performs the primary energy conversion steps of oxygenic photosynthesis. While the PSII-RC has been studied extensively, the similar timescales of energy transfer and charge separation, and the severely overlapping pigment transitions in the Qy region have led to multiple models of its charge separation mechanism and excitonic structure. Here we combine two-dimensional electronic spectroscopy (2DES) with a continuum probe and two-dimensional electronic vibrational spectroscopy (2DEV) to study the cyt b559-D1D2 PSII-RC at 77K. This multispectral comb…
Efficiency of energy funneling in the photosystem II supercomplex of higher plants
光合多蛋白质网络中能量传递特性的研究有助于深入了解其设计原理。本文讨论了高等植物光合机构中最大的功能单元--光系统II（PS-II）C $_2$ S $_2$ M $_2$超复合体的激子能量传递机制。尽管C $_2$ S $_2$ M $_2$中缺乏决定性的能量梯度，我们表明，能量转移是由弛豫指向低能态。C $_2$ S $_2$ M $_2$没有被组织成形成具有严格的能量向下转移的途径，这对转移效率、转移途径和转移限制步骤具有直接的后果。激子动力学对小的结构变化很敏感，例如，由振动坐标的重组引起的结构变化。为了将重组过程中，我们的数值模拟，我们超越速率方程，并使用分层耦合运动方程的方法（HEOM）。虽然从外周天线到反应中心附近的蛋白质的转移发生在更快的时间尺度上，但能量转移到RC核心的最后一步相当慢，因此是转移链中的限制步骤。我们的研究结果表明，PS-II超复合物的结构保证光保护，而不是优化效率。
In this work we study the first step in photosynthesis for the limiting case of a single photon interacting with photosystem II (PSII). We model our system using quantum trajectory theory, which allows us to consider not only the average evolution, but also the conditional evolution of the system given individual realizations of idealized measurements of photons that have been absorbed and subsequently emitted as fluorescence. The quantum nature of the single photon input requires a fully quantum model of both the input and output light fields. We show that PSII coupled to the field via three …
We report two-dimensional electronic spectroscopy (2DES) experiments on the bacterial reaction center (BRC) from purple bacteria, revealing hidden excitonic and vibronic structure. Through analysis of the coherent dynamics of the BRC we resolve specific coherent signatures that allow us to definitively assign the upper exciton energy of the "special pair." This assignment is supported by simulations of coherent dynamics of a reduced excitonic model of the BRC. The simulations also identify nonsecular vibronic coherence transfer processes neglected in standard models of photosynthetic energy tr…
We investigate the effect of coherence to the excitation transfer efficiency (ETE) in photosynthetic bacteria Chlorobium Tepidum. We have modeled the monomer of Fenna-Matthews-Olson (FMO) complex as consisting of eight bacteriochlorophyll-a sites, while explicitly consider reaction center core complex (RCC) as an additional site. With the use of realistic bath spectrum and several dominant vibronic modes in the non-Markovian master equation, in an effective 9-site model, we have compared the ETE for an initial pure state and an initial mixed state. We observe that the initial pure state relaxe…
We present a study on the evolution of the Fenna-Matthews-Olson bacterial photosynthetic pigment-protein complex. This protein complex functions as an antenna. It transports absorbed photons - excitons - to a reaction center where photosynthetic reactions initiate. The efficiency of exciton transport is therefore fundamental for the photosynthetic bacterium's survival. We have reconstructed an ancestor of the complex to establish whether coherence in the exciton transport was selected for or optimized over time. We have also investigated on the role of optimizing free energy variation upon fol…
During the first steps of photosynthesis, the energy of impinging solar photons is transformed into electronic excitation energy of the light-harvesting biomolecular complexes. The subsequent energy transfer to the reaction center is understood in terms of exciton quasiparticles which move on a grid of biomolecular sites on typical time scales less than 100 femtoseconds (fs). Since the early days of quantum mechanics, this energy transfer is described as an incoherent Forster hopping with classical site occupation probabilities, but with quantum mechanically determined rate constants. This ort…
Excitation energy transfer (EET) and electron transfer (ET) are crucially involved in photosynthetic processes. In reality, the photosynthetic reaction center constitutes an open quantum system of EET and ET, which manifests an interplay of pigments, solar light and phonon baths. So far theoretical studies have been mainly based on master equation approaches in the Markovian condition. The non-Markovian environmental effect, which may play a crucial role, has not been sufficiently considered. In this work, we propose a mixed dynamic approach to investigate this open system. The influence of ph…
In this paper we outline a physically motivated framework for describing spin-selective recombination processes in chiral systems, from which we derive spin-selective reaction operators for recombination reactions of donor-bridge-acceptor molecules, where the electron transfer is mediated by chirality and spin-orbit coupling. In general the recombination process is selective only for spin-coherence between singlet and triplet states, and it is not in general selective for spin polarisation. We find that spin polarisation selectivity only arises in hopping mediated electron transfer. We describ…
