Coherence-enhanced light harvesting has not been directly observed experimentally, despite theoretical evidence that coherence can significantly enhance light-harvesting performance. The main experimental obstacle has been the difficulty in isolating the effect of coherence in the presence of confounding variables. Recent proposals for externally controlling coherence by manipulating the light's degree of polarization showed that coherent efficiency enhancements would be possible, but were restricted to light-harvesting systems weakly coupled to their environment. Here, we show that increases in system-bath coupling strength can amplify coherent efficiency enhancements, rather than suppress them. This result dramatically broadens the range of systems that could be used to conclusively demonstrate coherence-enhanced light harvesting or to engineer coherent effects into artificial light-harvesting devices.
Spectroscopic experiments have identified long-lived coherences in several light-harvesting systems, suggesting that coherent effects may be relevant to their performance. However, there is limited experimental evidence of coherence enhancing light-harvesting efficiency, largely due to the difficulty of turning coherences on and off to create an experimental control. Here, we show that coherence can indeed enhance light harvesting, and that this effect can be controlled. We construct a model system in which initial coherence can be controlled using the incident light, and which is significantl…
Several kinds of coherence have recently been shown to affect the performance of light-harvesting systems, in some cases significantly improving their efficiency. Here, we classify the possible mechanisms of coherent efficiency enhancements, based on the types of coherence that can characterise a light-harvesting system and the types of processes these coherences can affect. We show that enhancements are possible only when coherences and dissipative effects are best described in different bases of states. Our classification allows us to predict a previously unreported coherent enhancement mech…
Recent evidence suggests that quantum effects may have functional importance in biological light-harvesting systems. Along with delocalized electronic excitations, it is now suspected that quantum coherent interactions with certain near-resonant vibrations may contribute to light-harvesting performance. However, the actual quantum advantage offered by such coherent vibrational interactions has not yet been established. We investigate a quantum design principle, whereby coherent exchange of single energy quanta between electronic and vibrational degrees of freedom can enhance a light-harvesting…
We explore the feasibility of coherent control of excitonic dynamics in light harvesting complexes, analyzing the limits imposed by the open nature of these quantum systems. We establish feasible targets for phase and phase/amplitude control of the electronically excited state populations in the Fenna-Mathews-Olson (FMO) complex and analyze the robustness of this control with respect to orientational and energetic disorder, as well as decoherence arising from coupling to the protein environment. We further present two possible routes to verification of the control target, with simulations for …
We investigate the influence of static disorder and thermal excitations on excitonic energy transport in the light-harvesting apparatus of photosynthetic systems by solving the Schrödinger equation and taking into account the coherent hoppings of excitons, the rates of exciton creation and annihilation in antennas and reaction centers, and the coupling to thermally excited phonons. The antennas and reaction centers are modeled, respectively, as the sources and drains which provide the channels for creation and annihilation of excitons. Phonon modes below a maximum frequency are coupled to the …
The influence of fast vibrations on energy transfer and conversion in natural molecular aggregates is an issue of central interest. This article shows the important role of high-energy quantized vibrations and their non-equilibrium dynamics for energy transfer in photosynthetic systems with highly localized excitonic states. We consider the cryptophyte antennae protein phycoerythrin 545 and show that coupling to quantized vibrations which are quasi-resonant with excitonic transitions is fundamental for biological function as it generates non-cascaded transport with rapid and wider spatial dist…
The efficiency of natural light harvesting systems is largely determined by their ability to transfer excitations from the antenna to the energy trapping center before recombination. Exciton diffusion length similarly limits organic photovoltaics and demands bulk heterojunction architectures. Dark state protection, achieved by coherent coupling between subunits within the antenna, can significantly reduce radiative recombination and enhance the efficiency of energy trapping. In this work we extend the dark state concept to the double-excitation manifold by studying the dynamical flow of excita…
Experimental and theoretical evidence point out to the crucial role of specific resonant intramolecular vibrational modes in the interpretation of long-lived coherences observed in two-dimensional spectra of some natural and synthetic light harvesting complexes. For the natural situation of illumination by incoherent (sun)light, the relevance of these vibrations is analyzed here for light-harvesting vibronic prototype dimers. The detailed analysis of the density matrix dynamics reveals that the inclusion of the intramolecular vibrational modes reinforce up to one order of magnitude the exciton…
Photosynthetic complexes improve the transfer of excitation energy from peripheral antennas to reaction centers in several ways. In particular, a downward energy funnel can direct excitons in the right direction, while coherent excitonic delocalization can enhance transfer rates through the cooperative phenomenon of supertransfer. However, isolating the role of purely coherent effects is difficult because any change to the delocalization also changes the energy landscape. Here, we show that the relative importance of the two processes can be determined by comparing the natural light-harvesting…
A vibronic exciton model is developed to investigate the origin of long lived coherences in light-harvesting complexes. Using experimentally determined parameters and uncorrelated site energy fluctuations, the model predicts oscillations in the nonlinear spectra of the Fenna-Matthews-Olson (FMO) complex with a dephasing time of 1.3 ps at 77 K. These oscillations correspond to the coherent superposition of vibronic exciton states with dominant contributions from vibrational excitations on the same pigment. Purely electronic coherences are found to decay on a 200 fs timescale.
The control of open quantum systems has a fundamental relevance for fields ranging from quantum information processing to nanotechnology. Typically, the system whose coherent dynamics one wants to manipulate, interacts with an environment that smoothly degrades its quantum dynamics. Thus, a precise understanding of the inner mechanisms of this process, called "decoherence", is critical to develop strategies to control the quantum dynamics. In this thesis we solved the generalized Liouville-von Neumann quantum master equation to obtain the dynamics of many-spin systems interacting with a spin b…
The observed prevalence of oscillatory signals in the spectroscopy of biological light-harvesting complexes at ambient temperatures has led to a search for mechanisms supporting coherent transport through larger molecules in noisy environments. We demonstrate a generic mechanism supporting long-lasting electronic coherence up to 0.3 ps at a temperature of 277 K. The mechanism relies on two properties of the spectral density: (i) a large dissipative coupling to a continuum of higher-frequency vibrations required for efficient transport and (ii) a small slope of the spectral density at zero freq…
The remarkable rotational symmetry of the photosynthetic antenna complexes of purple bacteria has long been thought to enhance their light harvesting and excitation energy transport. We study the role of symmetry by modeling hypothetical antennas whose symmetry is broken by altering the orientations of the bacteriochlorophyll pigments. We find that in both LH2 and LH1 complexes, symmetry increases energy transfer rates by enabling the cooperative, coherent process of supertransfer. The enhancement is particularly pronounced in the LH1 complex, whose natural geometry outperforms the average ran…
Until recently it was believed that photosynthesis, a fundamental process for life on earth, could be fully understood with semi-classical models. However, puzzling quantum phenomena have been observed in several photosynthetic pigment-protein complexes, prompting questions regarding the nature and role of these effects. Recent attention has focused on discrete vibrational modes that are resonant or quasi-resonant with excitonic energy splittings and strongly coupled to these excitonic states. Here we unambiguously identify excited state coherent superpositions in photosynthetic light-harvesti…
Recent ultrafast optical experiments show that excitons in large biological light-harvesting complexes are coupled to molecular vibration modes. These high-frequency vibrations will not only affect the optical response, but also drive the exciton transport. Here, using a model dimer system, the frequency of the underdamped vibration is shown to have a strong effect on the exciton dynamics such that quantum coherent oscillations in the system can be present even in the case of strong noise. Two mechanisms are identified to be responsible for the enhanced transport efficiency: critical damping d…
It has been suggested that excitation transport in photosynthetic light harvesting complexes features speedups analogous to those found in quantum algorithms. Here we compare the dynamics in these light harvesting systems to the dynamics of quantum walks, in order to elucidate the limits of such quantum speedups. For the Fenna-Matthews-Olson (FMO) complex of green sulfur bacteria, we show that while there is indeed speedup at short times, this is short lived (70 fs) despite longer lived (ps) quantum coherence. Remarkably, this time scale is independent of the details of the decoherence model. …
Several recent studies of energy transfer in photosynthetic light harvesting complexes have revealed a subtle interplay between coherent and decoherent dynamic contributions to the overall transfer efficiency in these open quantum systems. In this work we systematically investigate the impact of temporal and spatial correlations in environmental fluctuations on excitation transport in the Fenna-Matthews-Olson photosynthetic complex. We demonstrate that the exact nature of the correlations can have a large impact on the efficiency of light harvesting. In particular, we find that (i) spatial cor…
The prospect of coherent dynamics and excitonic delocalization across several light-harvesting structures in photosynthetic membranes is of considerable interest, but challenging to explore experimentally. Here we demonstrate theoretically that the excitonic delocalization across extended domains involving several light-harvesting complexes can lead to unambiguous signatures in the optical response, specifically, linear absorption spectra. We characterize, under experimentally established conditions of molecular assembly and protein-induced inhomogeneities, the optical absorption in these arra…
Electronic 2D spectroscopy allows nontrivial quantum effects in chemistry and biology to be explored in unprecedented detail. Here, we apply recently developed fluorescence detected coherent 2D spectroscopy to study the light harvesting antenna 2 (LH2) of photosynthetic purple bacteria. The method utilizes the destructive interference between two signal components thereby uncovering cross peaks which are not visible in conventional photon-echo based 2D and transient absorption measurements. Analyses of signal generating quantum pathways leads to the conclusion that, contrary to the currently p…
Nanoplasmonics has been used to enhance molecular spectroscopic signals, with exquisite spatial resolution down to the sub-molecular scale. By means of a rigorous, state-of-the-art multiscale model based on a quantum chemical description, here we show that optimally tuned tip-shaped metal nanoparticles can selectively excite localized regions of typically coherent systems, eventually narrowing down to probing one single pigment. The well-known major light-harvesting complex LH2 of purple bacteria has been investigated because of its unique properties, as it presents both high and weak delocali…
Elucidating quantum coherence effects and geometrical factors for efficient energy transfer in photosynthesis has the potential to uncover non-classical design principles for advanced organic materials. We study energy transfer in a linear light-harvesting model to reveal that dimerized geometries with strong electronic coherences within donor and acceptor pairs exhibit significantly improved efficiency, which is in marked contrast to predictions of the classical Förster theory. We reveal that energy tuning due to coherent delocalization of photoexcitations is mainly responsible for the effici…
A Comparative Study of Coherent and Action-Detected 2D Electronic Spectroscopies of a Multichromophore Photosynthetic System
Lund University（隆德大学）；ICFO - Institut de Ciencies Fotoniques, The Barcelona Institute of Science and Technology（ICFO-光子科学研究所，巴塞罗那科学技术研究院）；Biology Centre CAS and Faculty of Science, University of South Bohemia（捷克科学院生物学中心与南波希米亚大学理学院）
Recently the quantum nature in the energy transport in solar cell and light-harvesting complexes have attracted much attention, as being triggered by the experimental observations. We model the light-harvesting complex (i.e., PEB50 dimer) as a quantum heat engine (QHE) and study the effect of the undamped intra-molecule vibrational modes on the coherent energy transfer process and quantum transport. We find that the exciton-vibration interaction has non-trivial contribution to the promotion of quantum yield as well as transport properties of the quantum heat engine at steady state, by enhancin…
A generic and intuitive model for coherent energy transport in multiple minima systems coupled to a quantum mechanical bath is shown. Using a simple spin-boson system, we illustrate how a generic donor-acceptor system can be brought into resonance using a narrow band of vibrational modes, such that the transfer efficiency of an electron-hole pair (exciton) is made arbitrarily high. Coherent transport phenomena in nature are of renewed interest since the discovery that a photon captured by the light-harvesting complex (LHC) in photosynthetic organisms can be conveyed to a chemical reaction cent…
Starting from the many-body Schrödinger equation, we derive a new type of Lindblad Master equations describing a cyclic exciton/electron dynamics in the light harvesting complex and the reaction center. These equations resemble the Master equations for the electric current in mesoscopic systems, and they go beyond the single-exciton description by accounting for the multi-exciton states accumulated in the antenna, as well as the charge-separation, fluorescence and photo-absorption. Although these effects take place on very different timescales, their inclusion is necessary for a consistent des…
Long lasting coherence in photosynthetic pigment-protein complexes has been observed even at physiological temperatures. Experiments have demonstrated quantum coherent behaviour in the long-time operation of the D-Wave quantum computer as well. Quantum coherence is the common feature between the two phenomena. An explanations for eight orders of magnitude discrepancy between the single flux qubit coherence time and the long-time quantum behaviour of an array of thousand flux qubits in the quantum computer was suggested within a theory where the flux qubits are coupled to an environment of part…
We provide a unified theoretical approach to the quantum dynamics of absorption of single photons and subsequent excitonic energy transfer in photosynthetic light-harvesting complexes. Our analysis combines a continuous mode <n>-photon quantum optical master equation for the chromophoric system with the hierarchy of equations of motion describing excitonic dynamics in presence of non-Markovian coupling to vibrations of the chromophores and surrounding protein. We apply the approach to simulation of absorption of single-photon coherent states by pigment-protein complexes containing between one …
Chlorosomes are the largest and most efficient natural light-harvesting antenna systems. They contain thousands of pigment molecules - bacteriochlorophylls (BChls)- that are organized into supramolecular aggregates and form a very efficient network for excitonic energy migration. Here, we present a theoretical study of excitation energy transfer (EET) in the chlorosome based on experimental evidence of the molecular assembly. Our model for the exciton dynamics throughout the antenna combines a stochastic time propagation of the excitonic wave function with molecular dynamics simulations of sup…
Unravelling the nature of energy transport in multi-chromophoric photosynthetic complexes is essential to extract valuable design blueprints for light-harvesting applications. Long-range exciton transport in such systems is facilitated by a combination of delocalized excitation wavefunctions (excitons) and remarkable exciton diffusivities. The unambiguous identification of the exciton transport, however, is intrinsically challenging due to the system's sheer complexity. Here we address this challenge by employing a novel spectroscopic lab-on-a-chip approach: A combination of ultrafast coherent…
We challenge the misconception that Bloch-Redfield equations are a less powerful tool than phenomenological Lindblad equations for modeling exciton transport in photosynthetic complexes. This view predominantly originates from an indiscriminate use of the secular approximation. We provide a detailed description of how to model both coherent oscillations and several types of noise, giving explicit examples. All issues with non-positivity are overcome by a consistent straightforward physical noise model. Herein also lies the strength of the Bloch-Redfield approach because it facilitates the anal…
There is a remarkable characteristic of photosynthesis in nature, that is, the energy transfer efficiency is close to 100%. Recently, due to the rapid progress made in the experimental techniques, quantum coherent effects have been experimentally demonstrated. Traditionally, the incoherent theories are capable of calculating the energy transfer efficiency, e.g., (generalized) Förster theory and modified Redfield theory. However, in order to describe the quantum coherent effects in photosynthesis, the coherent theories have been developed, such as hierarchical equation of motion, quantum path i…
Transport phenomena in organic, self-assembled molecular J-aggregates have long attracted a great deal of attention due to its potential role in designing novel organic photovoltaic devices. A large number of theoretical and experimental studies have been carried out describing excitonic energy transfer in J-aggregates under the assumption that excitons are induced by a coherent laser-light source or initialized by a localized excitation on a particular chromophore. However, these assumptions may not provide an accurate description to assess the efficiency of J-aggregates, particularly as buil…
The nature of excited states of open quantum systems produced by incoherent natural thermal light is analyzed based on a description of the generator of the dynamics. Natural thermal light is shown to generate long-lasting coherent dynamics because of (i) the super-Ohmic character of the radiation, and (ii) the absence of pure dephasing dynamics. In the presence of an environment, the long-lasting coherences induced by suddenly turned-on incoherent light dissipate and stationary coherences are established. As a particular application, dynamics in a subunit of the PC-645 light-harvesting comple…
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 heated debate. Here, we perform an experimental quantum simulation of photosynthetic energy transfer using nuclear magnetic resonance (NMR). We show that a…
Two distinct approaches, the Frenkel-Dirac time-dependent variation and the Haken-Strobl model, are adopted to study energy transfer dynamics in single-ring and double-ring light-harvesting systems in purple bacteria. It is found that inclusion of long-range dipolar interactions in the two methods results in significant increases in intra- or inter-ring exciton transfer efficiency. The dependence of exciton transfer efficiency on trapping positions on single rings of LH2 (B850) and LH1 is similar to that in toy models with nearest-neighbor coupling only. However, owing to the symmetry breaking…
Coherent coupling between spatially separated systems has long been explored as a necessary requirement for quantum information and cryptography. Recent discoveries suggest such phenomena appear in a much wider range of processes, including light-harvesting in photosynthesis. These discoveries have been facilitated by developments in coherent multi-dimensional spectroscopy (CMDS) that allow interactions between different electronic states to be identified in crowded spectra. For complex systems, however, spectral broadening and multiple overlapping peaks limit the ability to separate, identify…
The structure of Fenna-Matthews-Olson (FMO) light-harvesting complex has long been recognized as containing seven bacteriochlorophyll (BChl) molecules. Recently, an additional BChl molecule was discovered in the crystal structure of the FMO complex, which may serve as a link between baseplate and the remaining seven molecules. Here, we investigate excitation energy transfer (EET) process by simulating single-molecule pump-dump experiment in the eight-molecules complex. We adopt the coherent modified Redfield theory and non-Markovian quantum jump method to simulate EET dynamics. This scheme pro…
Dependence of energy relaxation and vibrational coherence on the location of light-harvesting chromoproteins in photosynthetic antenna protein complexes
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., {\bf 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 dynam…
Light harvesting processes are often computationally studied from a time-dependent viewpoint, in line with ultrafast coherent spectroscopy experiments. Yet, natural processes take place in the presence of incoherent light, which induces a stationary state. Such stationary states can be described using the eigenbasis of the molecular Hamiltonian, but for realistic systems a full diagonalization is prohibitively expensive. We propose three efficient computational approaches to obtaining the stationary state that circumvent system Hamiltonian diagonalization. The connection between the incoherent…
The measured multi-dimensional spectral response of different light harvesting complexes exhibits oscillatory features which suggest an underlying coherent energy transfer. However, making this inference rigorous is challenging due to the difficulty of isolating excited state coherences in highly congested spectra. In this work, we provide a coherent control scheme that suppresses ground state coherences, thus making rephasing spectra dominated by excited state coherences. We provide a benchmark for the scheme using a model dimeric system and numerically exact methods to analyze the spectral r…
Excitation of a model photosynthetic molecular aggregate by incoherent sunlight is systematically examined. For a closed system, the excited state coherence induced by the sunlight oscillates with an average amplitude that is inversely proportional to the excitonic gap, and reaches a stationary amplitude that depends on the temperature and coherence time of the radiation field. For an open system, the light-induced dynamical coherence relaxes to a static coherence determined by the non-canonical thermal distribution resulting from the entanglement with the phonon bath. The decay of the excited…
Recent observations of coherence in photosynthetic complexes have led to the question of whether quantum effects can occur in vivo, not under femtosecond laser pulses but in incoherent sunlight and at steady state, and, if so, whether the coherence explains the high exciton transfer efficiency. We distinguish several types of coherence and show that although some photosynthetic pathways are partially coherent processes, photosynthesis in nature proceeds through stationary states. This distinction allows us to rule out several mechanisms of transport enhancement in sunlight. In particular, alth…
The energy transfer processes and coherent phenomena in the fucoxanthin-chlorophyll protein complex, which is responsible for the light harvesting function in marine algae diatoms, were investigated at 77 K by using two-dimensional electronic spectroscopy. Experiments performed on the femtosecond and picosecond timescales led to separation of spectral dynamics, witnessing evolutions of coherence and population states of the system in the spectral region of ${\rm Q}_{y}$ transitions of chlorophylls $a$ and $c$. Analysis of the coherence dynamics allowed us to identify chlorophyll (Chl) $a$ and …
It was once purported that biological systems were far too warm and wet to support quantum phenomena mainly due to thermal effects disrupting quantum coherence. However recent experimental results and theoretical analyses have shown that thermal energy may assist, rather than disrupt, quantum coherence, especially in the dry hydrophobic interiors of biomolecules. Specifically, evidence has been accumulating for the necessary involvement of quantum coherence and entanglement between uniquely arranged chromophores in light harvesting photosynthetic complexes. Amazingly, the tubulin subunit prote…
How atoms and electrons in a molecule move during a chemical reaction and how rapidly energy is transferred to or from the surroundings can be studied with flashes of laser light. However, despite prolonged efforts to develop various coherent spectroscopic techniques, the lack of an all-encompassing method capable of both femtosecond time resolution and nanosecond relaxation measurement has hampered various applications of studying correlated electron dynamics and vibrational coherences in functional materials and biological systems. Here, we demonstrate that two broadband (>300 nm) synchroniz…
Natural and artificial light harvesting processes have recently gained new interest. Signatures of long lasting coherence in spectroscopic signals of biological systems have been repeatedly observed, albeit their origin is a matter of ongoing debate, as it is unclear how the loss of coherence due to interaction with the noisy environments in such systems is averted. Here we report experimental and theoretical verification of coherent exciton-vibrational (vibronic) coupling as the origin of long-lasting coherence in an artificial light harvester, a molecular J-aggregate. In this macroscopically…
