Distinguishing the roles of energy funnelling and delocalization in photosynthetic light harvesting

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 apparatus with counterfactual models in which the delocalization and the energy landscape are altered. Applied to the example of purple bacteria, our approach shows that although supertransfer does enhance the rates somewhat, the energetic funnelling plays the decisive role. Because delocalization has a minor role (and is sometimes detrimental), it is most likely not adaptive, being a side-effect of the dense chlorophyll packing that evolved to increase light absorption per reaction center

Environment-assisted quantum transport in ordered systems

Noise-assisted transport in quantum systems occurs when quantum time-evolution and decoherence conspire to produce a transport efficiency that is higher than what would be seen in either the purely quantum or purely classical cases. In disordered systems, it has been understood as the suppression of coherent quantum localisation through noise, which brings detuned quantum levels into resonance and thus facilitates transport. We report several new mechanisms of environment-assisted transport in ordered systems, in which there is no localisation to overcome and where one would naively expect that coherent transport is the fastest possible. Although we are particularly motivated by the need to understand excitonic energy transfer in photosynthetic light-harvesting complexes, our model is general---transport in a tight-binding system with dephasing, a source, and a trap---and can be expected to have wider application

Delocalisation enables efficient charge generation in organic photovoltaics, even with little to no energetic offset

Organic photovoltaics (OPVs) are promising candidates for solar-energy conversion, with device efficiencies continuing to increase. However, the precise mechanism of how charges separate in OPVs is not well understood because low dielectric constants produce a strong attraction between the charges, which they must overcome to separate. Separation has been thought to require energetic offsets at donor-acceptor interfaces, but recent materials have enabled efficient charge generation with small offsets, or with none at all in neat materials. Here, we extend delocalised kinetic Monte Carlo (dKMC) to develop a three-dimensional model of charge generation that includes disorder, delocalisation, and polaron formation in every step from photoexcitation to charge separation. Our simulations show that delocalisation dramatically increases charge-generation efficiency, partly by enabling excitons to dissociate in the bulk. Therefore, charge generation can be efficient even in devices with little to no energetic offset, including neat materials. Our findings demonstrate that the underlying quantum-mechanical effect that improves the charge-separation kinetics is faster and longer-distance hops between delocalised states, mediated by hybridised states of exciton and charge-transfer character

Environment-Assisted Quantum Transport in Ordered Systems

Noise-assisted transport in quantum systems occurs when quantum time evolution and decoherence conspire to produce a transport efficiency that is higher than what would be seen in either the purely quantum or purely classical cases. In disordered systems, it has been understood as the suppression of coherent quantum localization through noise, which brings detuned quantum levels into resonance and thus facilitates transport. We report several new mechanisms of environment-assisted transport in ordered systems, in which there is no localization to overcome and where one would naively expect that coherent transport is the fastest possible. Although we are particularly motivated by the need to understand excitonic energy transfer in photosynthetic light-harvesting complexes, our model is general—transport in a tight-binding system with dephasing, a source and a trap—and can be expected to have wider application.Chemistry and Chemical Biolog

Benchmarking calculations of excitonic couplings between bacteriochlorophylls

Excitonic couplings between (bacterio)chlorophyll molecules are necessary for simulating energy transport in photosynthetic complexes. Many techniques for calculating the couplings are in use, from the simple (but inaccurate) point-dipole approximation to fully quantum-chemical methods. We compared several approximations to determine their range of applicability, noting that the propagation of experimental uncertainties poses a fundamental limit on the achievable accuracy. In particular, the uncertainty in crystallographic coordinates yields an uncertainty of about 20% in the calculated couplings. Because quantum-chemical corrections are smaller than 20% in most biologically relevant cases, their considerable computational cost is rarely justified. We therefore recommend the electrostatic TrEsp method across the entire range of molecular separations and orientations because its cost is minimal and it generally agrees with quantum-chemical calculations to better than the geometric uncertainty. We also caution against computationally optimizing a crystal structure before calculating couplings, as it can lead to large, uncontrollable errors. Understanding the unavoidable uncertainties can guard against striving for unrealistic precision; at the same time, detailed benchmarks can allow important qualitative questions--which do not depend on the precise values of the simulation parameters--to be addressed with greater confidence about the conclusions

Enhancing quantum transport in a photonic network using controllable decoherence

Transport phenomena on a quantum scale appear in a variety of systems, ranging from photosynthetic complexes to engineered quantum devices. It has been predicted that the efficiency of quantum transport can be enhanced through dynamic interaction between the system and a noisy environment. We report the first experimental demonstration of such environment-assisted quantum transport, using an engineered network of laser-written waveguides, with relative energies and inter-waveguide couplings tailored to yield the desired Hamiltonian. Controllable decoherence is simulated via broadening the bandwidth of the input illumination, yielding a significant increase in transport efficiency relative to the narrowband case. We show integrated optics to be suitable for simulating specific target Hamiltonians as well as open quantum systems with controllable loss and decoherence.Comment: 6 pages, 3 figure