Do quantum computers already exist in Nature? It is proposed that they do. Photosynthesis is one example in which a 'quantum computer' component may play a role in the 'classical' world of complex biological systems. A 'translation' of the standard metabolic description of the 'front-end' light harvesting complex in photosynthesis into the language of quantum computers is presented. Biological systems represent an untapped resource for thinking about the design and operation of hybrid quantum-classical computers and expanding our current conceptions of what defines a 'quantum computer' in Nature.
The long-standing problem of nearly perfect photosynthetic yield in some types of bacteria and nearly all kinds of plants despite the interaction with a hot and noisy environment has witnessed quantum optical explanations in the last decade or so. Typically in these explanations, photosynthetic reaction centers are modeled as five-level quantum heat engines where the generation of Fano-type interference due to the coupling of discrete state transitions with a common Markovian reservoir is held responsible for the enhancement of the photosynthetic efficiency. In this work, we go beyond the Born…
Photosynthesis is an important and complex physical process in nature, whose comprehensive understanding would have many relevant industrial applications, for instance in the field of energy production. In this paper we propose a quantum algorithm for the simulation of the excitonic transport of energy, occurring in the first stage of the process of photosynthesis. The algorithm takes in account the quantum and environmental effects (pure-dephasing), influencing the quantum transport. We performed quantum simulations of such phenomena, for a proof of concept scenario, in an actual quantum comp…
Open quantum system approaches are widely used in the description of physical, chemical and biological systems. A famous example is electronic excitation transfer in the initial stage of photosynthesis, where harvested energy is transferred with remarkably high efficiency to a reaction center. This transport is affected by the motion of a structured vibrational environment, which makes simulations on a classical computer very demanding. Here we propose an analog quantum simulator of complex open system dynamics with a precisely engineered quantum environment. Our setup is based on superconduct…
Transport phenomena in photosynthetic systems have attracted a great deal of attention due to their potential role in devising novel photovoltaic materials. In particular, energy transport in light-harvesting complexes is considered quite efficient due to the balance between coherent quantum evolution and decoherence, a phenomenon coined Environment-Assisted Quantum Transport (ENAQT). Although this effect has been extensively studied, its behavior is typically described in terms of the decoherence's strength, namely weak, moderate or strong. Here, we study the ENAQT in terms of quantum correla…
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 …
Recent experiments have demonstrated strong coupling between living bacteria and light. Here we propose a scheme capable of revealing non-classical features of the bacteria (quantum discord of light-bacteria correlations) without exact modelling of the organisms and their interactions with external world. The scheme puts the bacteria in a role of mediators of quantum entanglement between otherwise non-interacting probing light modes. We then propose a plausible model of this experiment, using recently achieved parameters, demonstrating the feasibility of the scheme. Within this model we find t…
We model energy transfer between two coupled four-level chromophores with arbitrarily spaced energy levels. Our analysis takes into account the crucial---yet often ignored---process of initial excitation by light that is incident on the chromophores. We show that the amount of entanglement generated between the chromophores is strongly dependent on the degree of initial excitation as well as the inclusion of higher energy levels. We apply our model to the specific example of chlorophyll. Our results suggest that an excitation-dependent approach should be employed for entanglement studies on mu…
The non-hermitian quantum dynamics of excitonic energy transfer in photosynthetic systems is investigated using a dissipative two-level dimer model. The approach is based on the Green's function formalism which permits consideration of decoherence and intersite transfer processes on comparable terms. The results indicate a combination of coherent and incoherent behavior at higher temperatures with the possibility of exceptional points occurring at the coherent-incoherent crossover regime at critical temperatures. When each dimer site is coupled equally to the environmental sources of dissipati…
We theoretically investigate exciton relaxation dynamics in molecular aggregates based on model photosynthetic complexes under various conditions of incoherent excitation. We show that noise-induced quantum coherence is generated between spatially-separated exciton states which belong to the same or different energy transfer pathways, coupled via real and virtual transfer processes. Such quantum coherence effects may be used to improve light-harvesting efficiency and to reveal quantum phenomena in biology.
Experimental/theoretical evidence for sustained vibration-assisted electronic (vibronic) coherence in the Photosystem II Reaction Center (PSII RC) indicates that photosynthetic solar-energy conversion might be optimized through the interplay of electronic and vibrational quantum dynamics. This evidence has been obtained by investigating the primary charge separation process in the PSII RC by two-dimensional electronic spectroscopy (2DES) and Redfield modeling of the experimental data. However, while conventional Fourier transform analysis of the 2DES data allows oscillatory signatures of vibro…
Assessing the role of interference in natural and artificial quantum dyanamical processes is a crucial task in quantum information theory. To this aim, an appopriate formalism is provided by the decoherent histories framework. While this approach has been deeply explored from different theoretical perspectives, it still lacks of a comprehensive set of tools able to concisely quantify the amount of coherence developed by a given dynamics. In this paper we introduce and test different measures of the (average) coherence present in dissipative (Markovian) quantum evolutions, at various time scale…
Chemically induced dynamic nuclear polarization is a ubiquitous phenomenon in photosynthetic reaction centers. The relevant nuclear spin observables are a direct manifestation of the radical-pair mechanism. We here use quantum trajectories to describe the time evolution of radical-pairs, and compare their prediction of nuclear spin observables to the one derived from the radical-pair master equation. While our approach provides a consistent description, we unravel a major inconsistency within the conven- tional theory, thus challenging the theoretical interpretation of numerous CIDNP experimen…
We investigate the quantum dynamics of energy and charge transfer in a wheel-shaped artificial photosynthetic antenna-reaction center complex.This complex consists of six light-harvesting chromophores and an electron-acceptor fullerene. To describe quantum effects on a femtosecond time scale, we derive the set of exact non-Markovian equations for the Heisenberg operators of this photosynthetic complex in contact with a Gaussian heat bath. With these equations we can analyze the regime of strong system-bath interactions, where reorganization energies are of the order of the intersite exciton co…
Despite several different measures of efficiency that are applicable to the photosynthetic systems, a precise degree of efficiency of these systems is not completely determined. Introducing an efficient model for the dynamics of light-harvesting complexes in biological environments is a major purpose in investigating such systems. Here, we investigate the effect of macroscopic quantum behavior of a system of two pigments on the transport phenomena in this system model which interacts with an oscillating environment. We use the second-order perturbation theory to calculate the time-dependent po…
Underlying physical principles for the high efficiency of excitation energy transfer in light-harvesting complexes are not fully understood. Notably, the degree of robustness of these systems for transporting energy is not known considering their realistic interactions with vibrational and radiative environments within the surrounding solvent and scaffold proteins. In this work, we employ an efficient technique to estimate energy transfer efficiency of such complex excitonic systems. We observe that the dynamics of the Fenna-Matthews-Olson (FMO) complex leads to optimal and robust energy trans…
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…
The Fenna-Matthews-Olson (FMO) antennae complex, responsible for light harvesting in green sulfur bacteria, consists of three monomers, each with seven chromophores. Here we show that multiple subsystems of the seven chromophores can transfer energy from either chromophore 1 or 6 to the reaction center with an efficiency matching or in many cases exceeding that of the full seven chromophore system. In the FMO complex these functional subsystems support multiple quantum pathways for efficient energy transfer that provide a built-in quantum redundancy. There are many instances of redundancy in n…
The high internal quantum efficiency observed in higher plants remains an outstanding problem in understanding photosynthesis. Several approaches such as quantum entanglement and quantum coherence have been explored. However, none has yet drawn an analogy between superlattices and the geometrical structure of granal thylakoids in leaves. In this paper, we calculate the transmission coefficients and perform numerical simulations using the parameters relevant to a stack of thylakoid discs. We then show that quantum resonant tunneling can occur at low effective mass of particles for 680 nm and 70…
Chemically induced dynamic nuclear polarization is a signature of spin order appearing in many photosynthetic reaction centers. Such polarization, significantly enhanced above thermal equilibrium, is known to result from the nuclear spin sorting inherent in the radical pair mechanism underlying long-lived charge-separated states in photosynthetic reaction centers. We will here show that the recently understood fundamental quantum dynamics of radical-ion-pair reactions open up a new and completely unexpected venue towards obtaining CIDNP signals. The fundamental decoherence mechanism inherent i…
Recently, several works have analysed the efficiency of photosynthetic complexes in a transient scenario and how that efficiency is affected by environmental noise. Here, following a quantum master equation approach, we study the energy and excitation transport in fully connected networks both in general and in the particular case of the Fenna-Matthew-Olson complex. The analysis is carried out for the steady state of the system where the excitation energy is constantly "flowing" through the system. Steady state transport scenarios are particularly relevant if the evolution of the quantum syste…
We develop a quantum scattering model to describe the exciton transport through the Fenna-Matthews-Olson(FMO) complex. It is found that the exciton transport involved the optimal quantum coherence is more efficient than that involved classical behavior alone. Furthermore, we also find that the quantum resonance condition is easier to be fulfilled in multiple pathways than that in one pathway. We then definitely demonstrate that the optimal distribution of the pigments, the multitude of energy delivery pathways and the quantum effects, are combined together to contribute to the perfect energy t…
Light harvesting components of photosynthetic organisms are complex, coupled, many-body quantum systems, in which electronic coherence has recently been shown to survive for relatively long time scales despite the decohering effects of their environments. Within this context, we analyze entanglement in multi-chromophoric light harvesting complexes, and establish methods for quantification of entanglement by presenting necessary and sufficient conditions for entanglement and by deriving a measure of global entanglement. These methods are then applied to the Fenna-Matthews-Olson (FMO) protein to…
Photosynthetic antenna complexes are responsible for absorbing energy from sunlight and transmitting it to remote locations where it can be stored. Recent experiments have found that this process involves long-lived quantum coherence between pigment molecules, called chromophores, which make up these complexes. Expected to decay within 100 fs at room temperature, these coherences were instead found to persist for picosecond time scales, despite having no apparent isolation from the thermal environment of the cell. This paper derives a quantum master equation which describes the coherent evolut…
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. …
Answering the titular question has become a central motivation in the field of quantum biology, ever since the idea was raised following a series of experiments demonstrating wave-like behavior in photosynthetic complexes. Here, we report a direct evaluation of the effect of quantum coherence on the efficiency of three natural complexes. An open quantum systems approach allows us to simultaneously identify their level of "quantumness" and efficiency, under natural physiological conditions. We show that these systems reside in a mixed quantum-classical regime, characterized by dephasing-assiste…
We propose a scheme to simulate the exciton energy transfer (EET) of photosynthetic complexes in a quantum superconducting circuit system. Our system is composed of two pairs of superconducting charge qubits coupled to two separated high-Q superconducting transmission line resonators (TLRs) connected by a capacitance. When the frequencies of the qubits are largely detuned with those of the TLRs, we simulate the process of the EET from the first qubit to the fourth qubit. By tuning the couplings between the qubits and the TLRs, and the coupling between the two TLRs, we can modify the effective …
The quantum network model with real variables is usually used to describe the excitation energy transfer (EET) in the Fenna-Matthews-Olson(FMO) complexes. In this paper we add the quantum phase factors to the hopping terms and find that the quantum phase factors play an important role in the EET. The quantum phase factors allow us to consider the space structure of the pigments. It is found that phase coherence within the complexes would allow quantum interference to affect the dynamics of the EET. There exist some optimal phase regions where the transfer efficiency takes its maxima, which ind…
We model the quantum electron transfer (ET) in the photosynthetic reaction center (RC), using a non-Hermitian Hamiltonian approach. Our model includes (i) two protein cofactors, donor and acceptor, with discrete energy levels and (ii) a third protein pigment (sink) which has a continuous energy spectrum. Interactions are introduced between the donor and acceptor, and between the acceptor and the sink, with noise acting between the donor and acceptor. The noise is considered classically (as an external random force), and it is described by an ensemble of two-level systems (random fluctuators). …
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…
We present a non-Markovian quantum jump approach for simulating coherent energy transfer dynamics in molecular systems in the presence of laser fields. By combining a coherent modified Redfield theory (CMRT) and a non-Markovian quantum jump (NMQJ) method, this new approach inherits the broad-range validity from the CMRT and highly efficient propagation from the NMQJ. To implement NMQJ propagation of CMRT, we show that the CMRT master equation can be casted into a generalized Lindblad form. Moreover, we extend the NMQJ approach to treat time-dependent Hamiltonian, enabling the description of ex…
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…
We review recent theoretical calculations of quantum entanglement in photosynthetic light harvesting complexes. These works establish, for the first time, a manifestation of this characteristically quantum mechanical phenomenon in biologically functional structures. We begin by summarizing calculations on model biomolecular systems that aim to reveal non-trivial characteristics of quantum entanglement in non-equilibrium biological environments. We then discuss and compare several calculations performed recently of excitonic dynamics in the Fenna-Matthews-Olson light harvesting complex and of t…
Energy transfer within photosynthetic systems can display quantum effects such as delocalized excitonic transport. Recently, direct evidence of long-lived coherence has been experimentally demonstrated for the dynamics of the Fenna-Matthews-Olson (FMO) protein complex [Engel et al., Nature 446, 782 (2007)]. However, the relevance of quantum dynamical processes to the exciton transfer efficiency is to a large extent unknown. Here, we develop a theoretical framework for studying the role of quantum interference effects in energy transfer dynamics of molecular arrays interacting with a thermal ba…
We analyze several aspects of the transport dynamics in the LH1-RC core of purple bacteria, which consists basically in a ring of antenna molecules that transport the energy into a target molecule, the reaction center, placed in the center of the ring. We show that the periodicity of the system plays an important role to explain the relevance of the initial state in the transport efficiency. This picture is modified, and the transport enhanced for any initial state, when considering that molecules have different energies, and when including their interaction with the environment. We study this…
Artificially reproducing the biological light reactions responsible for the remarkably efficient photon-to-charge conversion in photosynthetic complexes represents a new direction for the future development of photovoltaic devices. Here, we develop such a paradigm and present a model photocell based on the nanoscale architecture of photosynthetic reaction centres that explicitly harnesses the quantum mechanical effects recently discovered in photosynthetic complexes. Quantum interference of photon absorption/emission induced by the dipole-dipole interaction between molecular excited states gua…
Photosynthesis is a highly efficient process, nearly 100 percent of the red photons falling on the surface of leaves reach the reaction center and get transformed into energy. Most theoretical studies on photosynthetic complexes focus mainly on the Fenna-Matthews-Olson complex obtained from green-sulfur bacteria. Quantum coherence was speculated to play a significant role in this very efficient transport process. However, recent reports indicate quantum coherence via exciton transport may not be as relevant as coherence originating via vibronic processes to Photosynthesis. Regardless of the or…
We present a detailed theoretical study of the transfer of electronic excitation energy through the Fenna-Matthews-Olson (FMO) pigment-protein complex, using the new developed modified scaled hierarchical approach [Shi Q. et al, J Chem Phys 2009, 130, 084105]. We show that this approach is computationally more efficient than the original hierarchical approach. The modified approach reduces the truncation levels of the auxiliary density operators and the correlation function. We provide a systematic study of how the number of auxiliary density operators and the higher-order correlation function…
Primitive photosynthetic cells appear over three billion years prior to any other more complex life-forms, thus it is reasonable to assume that Nature has designed a photosynthetic mechanism using minimal resources but honed to perfection under the action of evolution. A number of different quantum models have been proposed to understand the high degree of efficient energy transport, most of them are limited to the scenario of single-exciton. Here we present a study on the dynamics in light-harvesting complexes beyond the single exciton limit, and show how this model describes the energy trans…
Photosynthetic antenna complexes capture and concentrate solar radiation by transferring the excitation to the reaction center which stores energy from the photon in chemical bonds. This process occurs with near-perfect quantum efficiency. Recent experiments at cryogenic temperatures have revealed that coherent energy transfer - a wavelike transfer mechanism - occurs in many photosynthetic pigment-protein complexes (1-4). Using the Fenna-Matthews-Olson antenna complex (FMO) as a model system, theoretical studies incorporating both incoherent and coherent transfer as well as thermal dephasing p…
Understanding how the effectiveness of natural photosynthetic energy harvesting systems arises from the interplay between quantum coherence and environmental noise represents a significant challenge for quantum theory. Recently it has begun to be appreciated that discrete molecular vibrational modes may play an important role in the dynamics of such systems. As an alternative to computationally demanding numerical approaches, we present a microscopic mechanism by which intramolecular vibrations contribute to the efficiency and directionality of energy transfer. Excited vibrational states creat…
Recently, the dynamics simulation of light-harvesting complexes as an open quantum system, in the weak and strong coupling regimes, has received much attention. In this paper, we investigate a digital quantum simulation approach of the Fenna-Matthews-Olson (FMO) photosynthetic pigment-protein complex surrounded with a Markovian bath, i.e., memoryless, based on a nuclear magnetic resonance (NMR) quantum computer. For this purpose, we apply the decoupling(recoupling) method, which is turn off(on) the couplings and also Solovay-Kitaev techniques to decompose Hamiltonian and Lindbladians into effi…
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…
Giant strides in ultrashort laser pulse technology have enabled real-time observation of dynamical processes in complex molecular systems. Specifically, the discovery of oscillatory transients in the two-dimensional electronic spectra of photosynthetic systems stimulated a number of theoretical investigations exploring possible physical mechanisms of the remarkable quantum efficiency of light harvesting processes. However, the theories employed have reached a high degree of sophistication and have become complex, making it difficult to gain insights into microscopic processes and biologically …
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 …
The early steps of photosynthesis involve the photo-excitation of reaction centres (RCs) and light-harvesting (LH) units. Here, we show that the --historically overlooked-- excitonic delocalisation across RC and LH pigments results in a redistribution of dipole strengths that benefits the absorption cross section of the optical bands associated with the RC of several species. While we prove that this redistribution is robust to the microscopic details of the dephasing between these units in the purple bacterium Rhodospirillum rubrum, we are able to show that the redistribution witnesses a more…
Electron transfer (ET) between primary electron donors and acceptors is modeled in the photosystem II reaction center (RC). Our model includes (i) two discrete energy levels associated with donor and acceptor, interacting through a dipole-type matrix element and (ii) two continuum manifolds of electron energy levels ("sinks"), which interact directly with the donor and acceptor. Namely, two discrete energy levels of the donor and acceptor are embedded in their independent sinks through the corresponding interaction matrix elements. We also introduce classical (external) noise which acts simult…
Charge separation in light-harvesting complexes occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine (QHE). Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem {\rm II} reaction center (PS{\rm II} RC) to describe the charge separation. Our model mainly considers two charge-separation pathways more than that in the published literature. The two pathway…
We investigate the evolution of entanglement in the Fenna-Matthew-Olson (FMO) complex based on simulations using the scaled hierarchy equation of motion (HEOM) approach. We examine the role of multipartite entanglement in the FMO complex by direct computation of the convex roof optimization for a number of measures, including some that have not been previously evaluated. We also consider the role of monogamy of entanglement in these simulations. We utilize the fact that the monogamy bounds are saturated in the single exciton subspace. This enables us to compute more measures of entanglement ex…
Long-lived electronic coherences in various photosynthetic complexes at cryogenic and room temperature have generated vigorous efforts both in theory and experiment to understand their origins and explore their potential role to biological function. The ultrafast signals resulting from the experiments that show evidence for these coherences result from many contributions to the molecular polarization. Quantum process tomography (QPT) was conceived in the context of quantum information processing to characterize and understand general quantum evolution of controllable quantum systems, for examp…
When dealing with system-reservoir interactions in an open quantum system, such as a photosynthetic light-harvesting complex, approximations are usually made to obtain the dynamics of the system. One question immediately arises: how good are these approximations, and in what ways can we evaluate them? Here, we propose to use entanglement and a measure of non-Markovianity as benchmarks for the deviation of approximate methods from exact results. We apply two frequently-used perturbative but non-Markovian approximations to a photosynthetic dimer model and compare their results with that of the n…
This paper investigates the dynamics of excitonic transport in photocomplex LHCII, the primary component of the photosynthetic apparatus in green plants. The dynamics exhibits a strong interplay between coherent processes mediated by the excitonic Hamiltonian, and incoherent processes due to interactions with the environment. The spreading of the exciton over a single monomer is well described by a proper measure of delocalization that allows one to identify two relevant time scales. An exciton initially localized in one chromophore first spreads coherently to neighboring chromophores. During …
In 2D electronic spectroscopy studies, long-lived quantum beats have recently been observed in photosynthetic systems, and it has been suggested that the beats are produced by quantum mechanically mixed electronic and vibrational states. Concerning the electronic-vibrational quantum mixtures, the impact of protein-induced fluctuations was examined by calculating the 2D electronic spectra of a weakly coupled dimer with vibrational modes in the resonant condition [J. Chem. Phys. 142, 212403 (2015)]. This analysis demonstrated that quantum mixtures of the vibronic resonance are rather robust unde…
