Theoretical study on the exciton dynamics of coherent excitation energy transfer in the phycoerythrin 545 light-harvesting complex

The experimental observation of long-lived quantum coherence in the excitation energy transfer(EET)process of the several photosynthetic light-harvesting complexes at low and room temperatures has aroused hot debate.It challenges the common perception in the field of complicated pigment molecular systems and evokes considerable theoretical efforts to seek reasonable explanations.In this work,we investigate the coherent exciton dynamics of the phycoerythrin 545(PE545)complex.We use the dissipation equation of motion to theoretically investigate the effect of the local pigment vibrations on the population transfer process.The result indicates that the realistic local pigment vibrations do assist the energy transmission.We demonstrate the coherence between different pigment molecules in the PE545 system is an essential ingredient in the EET process among various sites.The coherence makes the excitation energy delocalized,which leads to the redistribution of the excitation among all the chromophores in the steady state.Furthermore,we investigate the effects of the complex high-frequency spectral density function on the exciton dynamics and find that the high-frequency Brownian oscillator model contributes most to the exciton dynamic process.The discussions on the local pigment vibrations of the Brownian oscillator model suggest that the local heterogeneous protein environments and the effects of active vibration modes play a significant role in coherent energy transport.     

Energy transfer between two aggregates in light-harvesting complexes

Energy transfer processes between two aggregates in a coupled chromophoric-pigment(protein)system are studied via the standard master equation approach.Each pigment of the two aggregates is modeled as a two-level system.The excitation energy is assumed to be transferred from the donor aggregate to the acceptor aggregate.The model can be used to theoretically simulate many aspects of light-harvesting complexes(LHCs).By applying the real bio-parameters of photosynthesis,we numerically investigate the efficiency of energy transfer(EET)between the two aggregates in terms of some factors,e.g.,the initial coherence of the donor aggregate,the coupling strengthes between the two aggregates and between different pigments,and the effects of noise from the environment.Our results provide evidence for that the actual numbers of pigments in the chromophoric rings of LHCs should be the optimum parameters for a high EET.We also give a detailed analysis of the effects of noise on the EET.     

Light absorption and excitation energy transfer calculations in primitive photosynthetic bacteria

In photosynthetic organisms, light energy is converted into chemical energy through the light absorption and excitation energy transfer (EET) processes. These processes start in light-harvesting complexes, which contain special photosynthetic pigments. The exploration of unique mechanisms in light-harvesting complexes is directly related to studies, such as artificial photosynthesis or biosignatures in astrobiology. We examined, through ab initio calculations, the light absorption and EET processes using cluster models of light-harvesting complexes in purple bacteria (LH2). We evaluated absorption spectra and energy transfer rates using the LH2 monomer and dimer models to reproduce experimental results. After the calibration tests, a LH2 aggregation model, composed of 7 or 19 LH2s aligned in triangle lattice, was examined. We found that the light absorption is red shifted and the energy transfer becomes faster as the system size increases. We also found that EET is accelerated by exchanging the central pigments to lower energy excited pigments. As an astrobiological application, we calculated light absorptions efficiencies of the LH2 in different photoenvironments.     

Single-shot ultrabroadband two-dimensional electronic spectroscopy of the light-harvesting complex LH2

Here we present two-dimensional (2D) electronic spectra of the light-harvesting complex LH2 from purple bacteria using coherent pulses with bandwidth of over 100 nm FWHM. This broadband excitation and detection has allowed the simultaneous capture of both the B800 and B850 bands using a single light source. We demonstrate that one laser pulse is sufficient to capture the entire 2D electronic spectrum with a high signal-to-noise ratio. At a waiting time of 800 fs, we observe population transfer from the B800 to B850 band as manifested by a prominent cross peak. These results will enable observation of the dynamics of biological systems across both ultrafast (<1 ps) and slower (>1 ms) timescales simultaneously.     

Quantum correlation dynamics in photosynthetic processes assisted by molecular vibrations

During the long course of evolution, nature has learnt how to exploit quantum effects. In fact, recent experiments reveal the existence of quantum processes whose coherence extends over unexpectedly long time and space ranges. In particular, photosynthetic processes in light-harvesting complexes display a typical oscillatory dynamics ascribed to quantum coherence. Here, we consider the simple model where a dimer made of two chromophores is strongly coupled with a quasi-resonant vibrational mode. We observe the occurrence of wide oscillations of genuine quantum correlations, between electronic excitations and the environment, represented by vibrational bosonic modes. Such a quantum dynamics has been unveiled through the calculation of the negativity of entanglement and the discord, indicators widely used in quantum information for quantifying the resources needed to realize quantum technologies. We also discuss the possibility of approximating additional weakly-coupled off-resonant vibrational modes, simulating the disturbances induced by the rest of the environment, by a single vibrational mode. Within this approximation, one can show that the off-resonant bath behaves like a classical source of noise.     

Sustainability of Environment‐Assisted Energy Transfer in Quantum Photobiological Complexes

It is shown that quantum sustainability is a universal phenomenon which emerges during environment‐assisted electronic excitation energy transfer (EET) in photobiological complexes (PBCs), such as photosynthetic reaction centers and centers of melanogenesis. We demonstrate that quantum photobiological systems must be sustainable for them to simultaneously endure continuous energy transfer and keep their internal structure from destruction or critical instability. These quantum effects occur due to the interaction of PBCs with their environment which can be described by means of the reduced density operator and effective non‐Hermitian Hamiltonian (NH). Sustainable NH models of EET predict the coherence beats, followed by the decrease of coherence down to a small, yet non‐zero value. This indicates that in sustainable PBCs, quantum effects survive on a much larger time scale than the energy relaxation of an exciton. We show that sustainable evolution significantly lowers the entropy of PBCs and improves the speed and capacity of EET.     

Exciton delocalization probed by excitation annihilation in the light-harvesting antenna LH2

Singlet-singlet annihilation is used to study exciton delocalization in the light harvesting antenna complex LH2 (B800-B850) from the photosynthetic purple bacterium Rhodobacter sphaeroides. The characteristic femtosecond decay constants of the high intensity isotropic and the low intensity anisotropy kinetics of the B850 ring are related to the hopping time tau(h) and the coherence length N(coh) of the exciton. Our analysis yields N(coh) = 2.8+/-0.4 and tau(h) = 0.27+/-0.05 ps. This approach can be seen as an extension to the concept of the spectroscopic ruler.     

紫细菌捕光天线LH2中的超快光物理研究

采用飞秒泵浦探测技术研究了紫细菌外周捕光天线LH2中的超快光动力学过程.从B800蓝侧的激发态动力学中观察到B800到B850的能量传递时间,实验结果与理论计算结果的差别说明激发B800时可能引起B850上激子带的直接激发,或存在由B800到B850上激子态的能量传递通道.在B800红侧激发的动力学过程中,漂白信号前端存在的一个快速光吸收信号主要来源于B850上激子带的直接激发.在天然RS601和突变体GM309的LH2中,800 nm激发时的动力学过程都表现为一个类似的光漂白过程,动力学曲线的衰减时间常量在天然LH2中明显快于突变体中,说明在GM309中B800到B850的激发能传递速率有所降低.而在845 nm激发下两个样品中的快过程类似,但慢过程在GM309中有所增快,激发态中的能量重新分布包括逆向的能量传递也受到类胡萝卜素微结构的影响.     

Anomalous energy transfer dynamics due to torsional relaxation in a conjugated polymer

In isolated conjugated polymers two explanations are in discussion for the redshift of the emission on a picosecond time scale-exciton energy transfer (EET) between conjugated segments along the chains and conformational changes of these segments themselves, i.e., torsional relaxation. In order to resolve this question we perform femtosecond time-resolved transient absorption measurements of the energy relaxation of poly[3-(2,5-dioctylphenyl)thiophene] in toluene solution. We show that torsional relaxation can be distinguished from EET by site-selectively exciting low-energy conjugated segments. We present a unified model that integrates EET and torsional dynamics. In particular, comparison to ultrafast depolarization measurements shows that torsional dynamics cannot be neglected when analyzing EET dynamics and furthermore reveals that the exciton extends itself by about 2 monomer units during torsional relaxation.     

Energy Transfer in the Light-Harvesting Complexes of Purple Bacteria

In this paper, we use a nonlinear decohering quantum model to study the initial step of photosynthesis which is an ultrafast transfer process of absorption the sunlight by light-harvesting complexes and electronic excitation transfer to the reaction center(RC). In this decohering model, the Hamiltonian of the system commutes with the systemenvironment interaction. We take B850 ring of light-harvesting complex II(LH-II) in purple bacteria as an example to calculate the efficiency of the energy transfer as a function of time. We find that the environmental noise can make the LH-II have stable energy transfer efficiency over a long time. This is to say that the environmental noise which is the decohering source has advantage of the energy transfer in the process of photosynthesis.     

Nanoscale Wave Patterns in Reactive Adsorbates with Attractive Lateral Interactions

A model of a hypothetical surface chemical reaction with lateral interactions between adsorbed particles is investigated. It shows stationary, standing, and traveling nanoscale structures which result from the competition between reactions, diffusion, and the phase transition caused by attractive lateral interactions. Internal fluctuations destroy the coherence of traveling structures and lead to a complex dynamics of interacting traveling wave fragments in this system.     

Quantum coherence dynamics of a three-level atom in a two-mode field

The correlated dynamics of a three-level atom resonantly coupled to an electromagnetic cavity field is calculated (Λ, V, and L models). A diagrammatic representation of quantum dynamics is proposed for these models. As an example, Λ-atom dynamics is examined to demonstrate how the use of conventional von Neumann’s reduction leads to internal decoherence (disentanglement-induced decoherence) and to the absence of atomic coherence under multiphoton excitation. The predicted absence of atomic coherence is inconsistent with characteristics of an experimentally observed atom-photon entangled state. It is shown that the correlated reduction of a composite quantum system proposed in [18] qualitatively predicts the occurrence and evolution of atomic coherence under multiphoton excitation if a seed coherence is introduced into any subsystem (the atom or a cavity mode).     

Energy Transfer in the Light-Harvesting Complexes of Purple Bacteria

In this paper, we use a nonlinear decohering quantum model to study the initial step of photosynthesis which is an ultrafast transfer process of absorption the sunlight by light-harvesting complexes and electronic excitation transfer to the reaction center (RC). In this decohering model, the Hamiltonian of the system commutes with the systemenvironment interaction. We take B850 ring of light-harvesting complex Ⅱ (LH-Ⅱ) in purple bacteria as an example to calculate the efficiency of the energy transfer as a function of time. We find that the environmental noise can make the LH-Ⅱ have stable energy transfer efficiency over a long time. This is to say that the environmental noise which is the decohering source has advantage of the energy transfer in the process of photosynthesis.     

捕光复合物中起源于电子-振动耦合的长时间相干

We theoretically investigate the evolutions of two-dimensional, third-order, nonlinear pho-ton echo rephasing spectra with population time by using an exact numerical path integral method. It is shown that for the same system, the coherence time and relaxation time of excitonic states are short, however, if the couplings of electronic and intra-pigment vibra-tional modes are considered, the coherence time and relaxation time of this vibronic states are greatly extended. It means that the couplings between electronic and vibrational modes play important roles in keeping long-lived coherence in light-harvesting complexes. Particularly, by using the method we can fix the transition path of the energy transfer in bio-molecular systems.     

量子相干态的二维电子光谱测量的原理、应用和发展

二维电子光谱是一种同时具有高的时间分辨率和光谱分辨率的非线性光谱学方法.它不仅可以对凝聚相分子复杂动力学过程进行直接测量,还可以测量不同电子态、电子态-振动态之间的量子相干过程.2007年,Flemming课题组利用二维电子光谱于低温77 K的条件下在捕光天线蛋白Fenna-Matthews-Olson中发现了能量传递过程存在量子相干现象.尽管后续的实验研究表明,该体系中实验观测到的量子相干现象不可能是由单纯的电子态相干引起的,然而这一实验现象的报道极大地激发了人们对天然或人工模拟光合系统中存在量子相干传能途径的探索,目前还是一个相当活跃的研究领域.本文旨在通过介绍二维电子光谱学原理、装置及其在光合作用体系能量传递中量子相干现象的应用,使二维电子光谱这种实验方法能够在更多的研究领域得以普及与推广.     

Single-molecule study of the electronic couplings in a circular array of molecules: light-harvesting-2 complex from Rhodospirillum molischianum

Applying single-molecule spectroscopic techniques allowed us to determine the mutual angles between the transition-dipole moments associated with optical transitions of the eight bacteriochlorophyll a molecules which form the so-called B800 ring of the light-harvesting-2 complex from Rhodospirillum molischianum. The orientation of the transition-dipole moment is a sensitive probe for the strength of the local intermolecular interactions because of the well-defined arrangement of the individual molecules within the B800 ring. Our data reveal that the strength of the electronic coupling between individual molecules in the ring is subjected to spatial as well as temporal variations.     

Coherence effect on decryption characteristics in message modulation type chaos secure communication systems using fiber-optic ring resonators

We numerically investigated the dependence of the decryption characteristics in a message modulation type chaos secure communication system using optical fiber ring resonators (OFRRs) on the coherence condition of carrier light. Since the output dynamics of OFRRs were formed on the basis of interference phenomenon among the circulated components in OFRRs, the coherence condition of input light affected inherently the OFRR output dynamics, resulting in the decryption characteristics. It was found that the decryption characteristics degraded as coherence length increased, i.e., as the spectral width of the input light decreased. The decryption characteristics also grew worse as the parameter differences between the transmitter and the receiver became larger.     

Enhanced coherence of weakly coupled lasers

We present the phase-locking and coherence properties between two weakly coupled lasers. We show how the degree of coherence between the two lasers can be enhanced by nearly 1 order of magnitude after taking into account the effects of coupling on both their phases as well as their amplitudes. Specifically, correlations between synchronized spikes in the amplitude dynamics and the phase dynamics of the lasers allow for an interference pattern with a fringe visibility of 90%, even when the coupling strength is far below the critical value and they are not phase locked.     

Multivariate analysis of single-molecule spectra: surpassing spectral diffusion

The full exploitation of single-molecule spectroscopy in disordered systems is often hampered by spectral diffusion processes of the optical transitions due to structural fluctuations in the local environment of the probe molecule which leads to temporal averaging of the signal. Multivariate statistical pattern recognition techniques, originally developed for single-molecule cryoelectron microscopy, allow us to retrieve detailed information from optical single-molecule spectra. As an example, we present the phonon side band of the B800 excitations of the light-harvesting 2 (LH2) complex from Rhodospirillum molischianum, revealing the electron-phonon coupling strength for these transitions. The measured Debye-Waller factors, ranging from 0.4 to 0.9, fall in the regime of weak electron-phonon coupling.     

Influence of LDAO on the conformation and release of bacteriochlorophyll of peripheral light-harvesting complex (LH2) from Rhodobacter azotoformans

The aim of this study is to reveal the interaction relationships between lauryl dimethylamine N-oxide (LDAO) and peripheral light-harvesting complex (LH2) as well as the influence of LDAO on structure and function of LH2. In the present work, the effects of LDAO on the conformation and release processes of bacteriochlorophyll (BChl) of LH2 when incubated under different temperature and pH in the presence and absence of LDAO were investigated by spectroscopy. The results indicated that (1) the presence of LDAO resulted in alterations in the conformation, alpha-helix content, and spectra of Tyr and B850 band of LH2 at room temperature and pH 8.0. Moreover, energy transfer efficiency of LH2 was enhanced markedly in the presence of LDAO. (2) At 60 degrees C, both the B800 and B850 band of LH2 were released and transited into free BChl at pH 8.0. However, the release rates of bacteriochlorophylls of B800 and B850 band from LH2 were slowed down and the release processes were changed when incubated in the presence of LDAO. Hence, the stability of LH2 was improved in the presence of LDAO. (3) The accelerated release processes of bacteriochlorophylls of B800 and B850 band of LH2 were induced to transform into bacteriopheophytin (BPhe) and free BChl by LDAO in strong acid and strong alkalic solution at room temperature. However, the kinetic patterns of the B800 and B850 band were remarkably different. The release and self-assemble processes of B850 in LH2 were observed in strong acid solution without LDAO. Therefore, the different release behaviors of B800 and B850 of LH2 are induced by LDAO under different extreme environmental conditions.