Solar fuel production often starts with the energy from light being absorbed by an assembly of molecules; this electronic excitation is subsequently transferred to a suitable acceptor. For example, in photosynthesis, antenna complexes capture sunlight and direct the energy to reaction centres that then carry out the associated chemistry. In this Review, we describe the principles learned from studies of various natural antenna complexes and suggest how to elucidate strategies for designing light-harvesting systems. We envisage that such systems will be used for solar fuel production, to direct and regulate excitation energy flow using molecular organizations that facilitate feedback and control, or to transfer excitons over long distances. Also described are the notable properties of light-harvesting chromophores, spatial-energetic landscapes, the roles of excitonic states and quantum coherence, as well as how antennas are regulated and photoprotected.

Lessons from nature about solar light harvesting

Quantum simulators are controllable quantum systems that can be used to mimic other quantum systems. They have the potential to enable the tackling of problems that are intractable on conventional computers. The photonic quantum technology available today is reaching the stage where significant advantages arise for the simulation of interesting problems in quantum chemistry, quantum biology and solid-state physics. In addition, photonic quantum systems also offer the unique benefit of being mobile over free space and in waveguide structures, which opens new perspectives to the field by enabling the natural investigation of quantum transport phenomena. Here, we review recent progress in the field of photonic quantum simulation, which should break the ground towards the realization of versatile quantum simulators. Quantum optics has played an important role in the exploration of foundational issues in quantum mechanics, and in using quantum effects for information processing and communications purposes. Photonic quantum systems now also provide a valuable test bed for quantum simulations. This article surveys the first generation of such experiments, and discusses the prospects for tackling outstanding problems in physics, chemistry and biology.

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Photonic quantum simulators

Aggregates of conjugated polymers exhibit two classes of fundamental electronic interactions: those occurring within a given chain and those occurring between chains. The impact of such excitonic interactions on the photophysics of polymer films can be understood using concepts of J- and H-aggregation originally developed by Kasha and coworkers to treat aggregates of small molecules. In polymer assemblies, intrachain through-bond interactions lead to J-aggregate behavior, whereas interchain Coulombic interactions lead to H-aggregate behavior. The photophysics of common emissive conjugated polymer films are determined by a competition between intrachain, J-favoring interactions and interchain, H-favoring interactions. We review formalisms describing absorption and photoluminescence lineshapes, based on intra- and intermolecular excitonic coupling, electron-vibrational coupling, and correlated energetic disorder. Examples include regioregular polythiophenes, pheneylene-vinylenes, and polydiacetylene.

H- and J-Aggregate Behavior in Polymeric Semiconductors

Quantum control is concerned with active manipulation of physical and chemical processes on the atomic and molecular scale. This work presents a perspective of progress in the field of control over quantum phenomena, tracing the evolution of theoretical concepts and experimental methods from early developments to the most recent advances. Among numerous theoretical insights and technological improvements that produced the present state-of- the-art in quantum control, there have been several breakthroughs of foremost importance. On the technology side, the current experimental successes would be impossible without the development of intense femtosecond laser sources and pulse shapers. On the theory side, the two most critical insights were (i) realizing that ultrafast atomic and molecular dynamics can be controlled via manipulation of quantum interferences and (ii) understanding that optimally shaped ultrafast laser pulses are the most effective means for producing the desired quantum interference patterns in the controlled system. Finally, these theoretical and experimental advances were brought together by the crucial concept of adaptive feedback control (AFC), which is a laboratory procedure employing measurement-driven, closed-loop optimization to identify the best shapes of femtosecond laser control pulses for steering quantum dynamics towards the desired objective. Optimization in AFC experiments is guided by a learning algorithm, with stochastic methods proving to be especially effective. AFC of quantum phenomena has found numerous applications in many areas of the physical and chemical sciences, and this paper reviews the extensive experiments. Other subjects discussed include quantum optimal control theory, quantum control landscapes, the role of theoretical control

https://iopscience.iop.org/article/10.1088/1367-2630/12/7/075008/pdf

Control of quantum phenomena: past, present and future

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
extract the initial state and temperature dependencies of entanglement. We show
that while FMO in natural conditions largely contains bipartite entanglement
between dimerized chromophores, a small amount of long-range and multipartite
entanglement exists even at physiological temperatures. This constitutes the
first rigorous quantification of entanglement in a biological system. Finally,
we discuss the practical utilization of entanglement in densely packed
molecular aggregates such as light harvesting complexes.

/pdf/quantum-entanglement-in-photosynthetic-light-harvesting-3i5e4q03pv.pdf

Quantum entanglement in photosynthetic light-harvesting complexes

Photosynthetic antenna complexes capture and concentrate solar radiation by transferring the excitation to the reaction center that 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 wave-like transfer mechanism—occurs in many photosynthetic pigment-protein complexes. 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 predict that environmentally assisted quantum transfer efficiency peaks near physiological temperature; these studies also show that this mechanism simultaneously improves the robustness of the energy transfer process. This theory requires long-lived quantum coherence at room temperature, which never has been observed in FMO. Here we present evidence that quantum coherence survives in FMO at physiological temperature for at least 300 fs, long enough to impact biological energy transport. These data prove that the wave-like energy transfer process discovered at 77 K is directly relevant to biological function. Microscopically, we attribute this long coherence lifetime to correlated motions within the protein matrix encapsulating the chromophores, and we find that the degree of protection afforded by the protein appears constant between 77 K and 277 K. The protein shapes the energy landscape and mediates an efficient energy transfer despite thermal fluctuations.

/pdf/long-lived-quantum-coherence-in-photosynthetic-complexes-at-2ykqpezlko.pdf

Long-lived quantum coherence in photosynthetic complexes at physiological temperature

The photosynthetic light-harvesting apparatus moves energy from absorbed photons to the reaction center with remarkable quantum efficiency. Recently, long-lived quantum coherence has been proposed to influence efficiency and robustness of photosynthetic energy transfer in light-harvesting antennae. The quantum aspect of these dynamics has generated great interest both because of the possibility for efficient long-range energy transfer and because biology is typically considered to operate entirely in the classical regime. Yet, experiments to date show only that coherence persists long enough that it can influence dynamics, but they have not directly shown that coherence does influence energy transfer. Here, we provide experimental evidence that interaction between the bacteriochlorophyll chromophores and the protein environment surrounding them not only prolongs quantum coherence, but also spawns reversible, oscillatory energy transfer among excited states. Using two-dimensional electronic spectroscopy, we observe oscillatory excited-state populations demonstrating that quantum transport of energy occurs in biological systems. The observed population oscillation suggests that these light-harvesting antennae trade energy reversibly between the protein and the chromophores. Resolving design principles evident in this biological antenna could provide inspiration for new solar energy applications.

/pdf/direct-evidence-of-quantum-transport-in-photosynthetic-light-38xj531c1i.pdf

Direct evidence of quantum transport in photosynthetic light-harvesting complexes

We present the first two-dimensional electronic spectra of photosynthetic antenna complexes bearing modifications to the protein and the chromophores. The vibronic structure of the Fenna–Matthews–Olson complex was altered by near-complete substitution of 13C for naturally abundant carbon and separately by randomly distributed partial deuteration. The structure and arrangement of the bacteriochlorophyllachromophores were modified by deletion of the gene encoding the enzyme responsible for reducing the isoprenoid tail of the bacteriochlorophylls. Analysis of the time-dependent amplitude of the crosspeak corresponding to excitons 1 and 2 indicates that these modifications do not affect the frequency or dephasing of the beating observed in this particular peak. This result leads us to conclude that this beating indeed arises from electronic coherence and not vibrational wavepacket motion. We further conclude that the protection of zero-quantum coherences afforded by the protein matrix of this photosynthetic complex is not the result of a finely-tuned series of system–bath interactions perfected by billions of years of evolution but rather a simple downstream property of a close arrangement of chromophores within a phonon bath. We conclude with a brief discussion of the outstanding questions and possible applications of this phenomenon.

Robustness of electronic coherence in the Fenna-Matthews-Olson complex to vibronic and structural modifications

Electronic coherence has been shown to persist in the Fenna?Matthews?Olson (FMO) antenna complex from green sulfur bacteria at 77?K for at least 660?fs, several times longer than the typical lifetime of a coherence in a dynamic environment at this temperature. Such long-lived coherence was proposed to improve energy transfer efficiency in photosynthetic systems by allowing an excitation to follow a quantum random walk as it approaches the reaction centre. Here we present a model for bath-induced electronic transitions, demonstrating that the protein matrix protects coherences by globally correlating fluctuations in transition energies. We also quantify the dephasing rates for two particular electronic coherences in the FMO complex at 77?K using two-dimensional Fourier transform electronic spectroscopy and find that the lifetimes of individual coherences are distinct. Within the framework of noise-assisted transport, this result suggests that the FMO complex has been locally tuned by natural selection to optimize transfer efficiency by exploiting quantum coherence.

https://iopscience.iop.org/article/10.1088/1367-2630/12/6/065042/pdf

Gitt Panitchayangkoon

Papers

Long-lived quantum coherence in photosynthetic complexes at physiological temperature

Direct evidence of quantum transport in photosynthetic light-harvesting complexes

Robustness of electronic coherence in the Fenna-Matthews-Olson complex to vibronic and structural modifications

Dynamics of electronic dephasing in the Fenna–Matthews–Olson complex