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Under physiological conditions, ballistic long-range transfer of electronic excitations in molecular aggregates is generally expected to be suppressed by noise and dissipative processes. Hence, quantum phenomena are not considered to be relevant for the design of efficient and controllable energy transfer over significant length scales and timescales. Contrary to this conventional wisdom, here we show that the robust quantum properties of small configurations of repeating clusters of molecules can be used to tune energy-transfer mechanisms that take place on much larger scales. With the support of an exactly solvable model, we demonstrate that coherent exciton delocalization and dark states within unit cells can be used to harness dissipative phenomena of varying nature (thermalization, fluorescence, nonradiative decay, and weak intersite correlations) to support classical propagation over macroscopic distances. In particular, we argue that coherent delocalization of electronic excitations over just a few pigments can drastically alter the relevant dissipation pathways that influence the energy-transfer mechanism and thus serve as a molecular control tool for large-scale properties of molecular materials. Building on these principles, we use extensive numerical simulations to demonstrate that they can explain currently not-understood measurements of micron-scale exciton diffusion in nanofabricated arrays of bacterial photosynthetic complexes. Based on these results, we provide quantum design guidelines at the molecular scale to optimize both energy-transfer speed and range over macroscopic distances in artificial light-harvesting architectures.

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 aligned tubular system, polarization-controlled 2D spectroscopy delivers an uncongested and specific optical response as an ideal foundation for an in-depth theoretical description. We derive analytical expressions that show under which general conditions vibronic coupling leads to prolonged excited-state coherence. Two-dimensional spectroscopy revealed oscillatory signals in photosynthesis’ exciton dynamics, but crowded spectra impede the identification of what sustains the oscillations. Here the authors probe an J-aggregate, whose uncongested response shows that vibronic coupling is responsible for the sustained coherence.

Photosynthetic systems utilize adaptability to respond efficiently to fluctuations in their light environment. As a result, large photosynthetic yields can be achieved in conditions of low light intensity, while photoprotection mechanisms are activated in conditions of elevated light intensity. In sharp contrast with these observations, current theoretical models predict bacterial cell death for physiologically high light intensities. To resolve this discrepancy, we consider a unified framework to describe three stages of photosynthesis in natural conditions, namely light absorption, exciton transfer and charge separation dynamics, to investigate the relationship between the statistical features of thermal light and the Quinol production in bacterial photosynthesis. This approach allows us to identify a mechanism of photoprotection that relies on charge recombination facilitated by the photon bunching statistics characteristic of thermal sunlight. Our results suggest that the flexible design underpinning natural photosynthesis may therefore rely on exploiting the temporal correlations of thermal light, manifested in photo-bunching patterns, which are preserved for excitations reaching the reaction center.

Under physiological conditions, ballistic long-range transfer of electronic excitations in molecular aggregates is generally expected to be suppressed by noise and dissipative processes. Hence, quantum phenomena are not considered to be relevant for the design of efficient and controllable energy transfer over significant length and time scales. Contrary to this conventional wisdom, here we show that the robust quantum properties of small configurations of repeating clusters of molecules can be used to tune energy transfer mechanism that take place on much larger scales. With the support of an exactly solvable model, we demonstrate that coherent exciton delocalization and dark states within unit cells can be used to harness dissipative phenomena of varying nature (thermalization, fluorescence, non-radiative decay and weak inter-site correlations) to support classical propagation over macroscopic distances. In particular, we argue that coherent delocalization of electronic excitations over just a few pigments can drastically alter the relevant dissipation pathways which influence the energy transfer mechanism, and thus serve as a molecular control tool for large-scale properties of molecular materials. Building on these principles, we use extensive numerical simulations to demonstrate that they can explain currently not understood measurements of micron-scale exciton diffusion in nano-fabricated arrays of bacterial photosynthetic complexes. Based on these results we provide quantum design guidelines at the molecular scale to optimize both energy transfer speed and range over macroscopic distances in artificial light-harvesting architectures.

We show that `which-way' interference within unit-cells enhances the propagation along linear arrays made upon these basic units. As a working example, we address the exciton transfer through linear aggregates of ring-like unit cells, the latter resembling the circular structure of the Light-Harvesting complexes of purple bacteria. After providing an analytic approximate solution of the eigenvalue problem for such aggregates, we show that the population transferred across the array is not a monotonic function of the coupling between nearest-neighbor rings, contrary to what is found from situations where this intra-unit cell interference is not displayed. The non-monotonicity depends on an interesting trade off between the exciton transfer speed and the amount of energy transferred, which is associated with the rupture of symmetry among paths within the ring-like cells, due to the inter-ring coupling strength.

A nanoring-rotaxane supramolecular assembly, with a Cy7 cyanine dye (hexamethylindotricarbocyanine) threaded along the axis of the nanoring, has been synthesized as a model for the energy transfer between the light harvesting complex LH1 and the reaction center in purple bacteria photosynthesis. The complex displays efficient energy transfer from the central cyanine dye to the surrounding zinc porphyrin nanoring. We present a theoretical model that reproduces the absorption spectrum of the nanoring and quantifies the excitonic coupling between the nanoring and the central dye, explaining the efficient energy transfer and elucidating the similarity with structurally related natural light harvesting systems.

Nonlinear spectroscopy has revealed long-lasting oscillations in the optical response of a variety of photosynthetic complexes. Different theoretical models which involve the coherent coupling of electronic (excitonic) or electronic-vibrational (vibronic) degrees of freedom have been put forward to explain these observations. The ensuing debate concerning the relevance of either one or the other mechanism may have obscured their potential synergy. To illustrate this synergy, we quantify how the excitonic delocalization in the LH2 unit of Rhodopseudomonas Acidophila purple bacterium, leads to correlations of excitonic energy fluctuations, relevant coherent vibronic coupling and, importantly, a decrease in the excitonic dephasing rates. Combining these effects, we identify a feasible origin for the long-lasting oscillations observed in fluorescent traces from time-delayed two-pulse single molecule experiments performed on this photosynthetic complex.

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 fragile, but persistent, coherent population dynamics which directs excitations from the LH towards the RC units under incoherent illumination and physiological conditions. Stochastic optimisation allows us to delineate clear guidelines and develop simple analytic expressions, in order to achieve directed coherent population dynamics in artificial nano-structures.

Photosynthetic systems utilize adaptability to respond efficiently to fluctuations in their light environment. As a result, large photosynthetic yields can be achieved in conditions of low light intensity, while photoprotection mechanisms are activated in conditions of elevated light intensity. In sharp contrast with these observations, current theoretical models predict bacterial cell death for physiologically high light intensities. To resolve this discrepancy, we consider a unified framework to describe three stages of photosynthesis in natural conditions, namely light absorption, exciton transfer and charge separation dynamics, to investigate the relationship between the statistical features of thermal light and the Quinol production in bacterial photosynthesis. This approach allows us to identify a mechanism of photoprotection that relies on charge recombination facilitated by the photon bunching statistics characteristic of thermal sunlight. Our results suggest that the flexible design underpinning natural photosynthesis may therefore rely on exploiting the temporal correlations of thermal light, manifested in photo-bunching patterns, which are preserved for excitations reaching the reaction center.

The promise of any small improvement in the performance of light-harvesting devices, is sufficient to drive enormous experimental efforts. However these efforts are almost exclusively focused on enhancing the power conversion efficiency with specific material properties and harvesting layers thickness, without exploiting the correlations present in sunlight -- in part because such correlations are assumed to have negligible effect. Here we show, by contrast, that these spatio-temporal correlations are sufficiently relevant that the use of specific detector geometries would significantly improve the performance of harvesting devices. The resulting increase in the absorption efficiency, as the primary step of energy conversion, may also act as a potential driving mechanism for artificial photosynthetic systems. Our analysis presents design guidelines for optimal detector geometries with realistic incident intensities based on current technological capabilities