Efficiency of energy transfer in a light-harvesting system under quantum coherence

We investigate the role of quantum coherence in the efficiency of excitation transfer in a ring-hub arrangement of interacting two-level systems, mimicking a light-harvesting antenna connected to a reaction center as it is found in natural photosynthetic systems. By using a quantum jump approach, we demonstrate that in the presence of quantum coherent energy transfer and energetic disorder, the efficiency of excitation transfer from the antenna to the reaction center depends intimately on the quantum superposition properties of the initial state. In particular, we find that efficiency is sensitive to symmetric and asymmetric superposition of states in the basis of localized excitations, indicating that initial state properties can be used as a efficiency control parameter at low temperatures.Comment: Extended version of original paper. 7 pages, 2 figure

Distribution of entanglement in light-harvesting complexes and their quantum efficiency

Recent evidence of electronic coherence during energy transfer in photosynthetic antenna complexes has reinvigorated the discussion of whether coherence and/or entanglement has any practical functionality for these molecular systems. Here we investigate quantitative relationships between the quantum yield of a light-harvesting complex and the distribution of entanglement among its components. Our study focusses on the entanglement yield or average entanglement surviving a time scale comparable to the average excitation trapping time. As a prototype system we consider the Fenna-Matthews-Olson (FMO) protein of green sulphur bacteria and show that there is an inverse relationship between the quantum efficiency and the average entanglement between distant donor sites. Our results suggest that longlasting electronic coherence among distant donors might help modulation of the lightharvesting function.Comment: Version accepted for publication in NJ

Non-Markovian stochastic description of quantum transport in photosynthetic systems

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 last situation by using stochastic Schr{\"o}dinger equations, both for Markovian and non-Markovian type of interactions.Comment: 21 pages, 5 figure

Multiscale photosynthetic exciton transfer

Photosynthetic light harvesting provides a natural blueprint for bioengineered and biomimetic solar energy and light detection technologies. Recent evidence suggests some individual light harvesting protein complexes (LHCs) and LHC subunits efficiently transfer excitons towards chemical reaction centers (RCs) via an interplay between excitonic quantum coherence, resonant protein vibrations, and thermal decoherence. The role of coherence in vivo is unclear however, where excitons are transferred through multi-LHC/RC aggregates over distances typically large compared with intra-LHC scales. Here we assess the possibility of long-range coherent transfer in a simple chromophore network with disordered site and transfer coupling energies. Through renormalization we find that, surprisingly, decoherence is diminished at larger scales, and long-range coherence is facilitated by chromophoric clustering. Conversely, static disorder in the site energies grows with length scale, forcing localization. Our results suggest sustained coherent exciton transfer may be possible over distances large compared with nearest-neighbour (n-n) chromophore separations, at physiological temperatures, in a clustered network with small static disorder. This may support findings suggesting long-range coherence in algal chloroplasts, and provides a framework for engineering large chromophore or quantum dot high-temperature exciton transfer networks.Comment: 9 pages, 6 figures. A significantly updated version is now published online by Nature Physics (2012

Noise-assisted energy transfer in quantum networks and light-harvesting complexes

'This is an author-created, un-copyedited version of an article accepted for publication in New Journal of Physics. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The definitive publisher authenticated version is available online at: http://dx.doi.org/10.1088/1367-2630/12/6/065002 .'We provide physically intuitive mechanisms for the effect of noise on excitation energy transfer (EET) in networks. Using these mechanisms of dephasing-assisted transport (DAT) in a hybrid basis of both excitons and sites, we develop a detailed picture of how noise enables energy transfer with efficiencies well above 90% across the Fenna–Matthew–Olson (FMO) complex, a type of light-harvesting molecule. We demonstrate explicitly how noise alters the pathways of energy transfer across the complex, suppressing ineffective pathways and facilitating direct ones to the reaction centre. We explain that the fundamental mechanisms underpinning DAT are expected to be robust with respect to the considered noise model but show that the specific details of the exciton–phonon coupling, which remain largely unknown in these type of complexes, and in particular the impact of non-Markovian effects, result in variations of dynamical features that should be amenable to experimental verification with current or planned technology. A detailed understanding of DAT in natural compounds could open up a new paradigm of 'noise-engineering' by which EET can be optimized in artificial light-harvesting structures.Peer reviewe

Energy Transfer in Light-Adapted Photosynthetic Membranes: From Active to Saturated Photosynthesis

In bacterial photosynthesis light-harvesting complexes, LH2 and LH1 absorb sunlight energy and deliver it to reaction centers (RCs) with extraordinarily high efficiency. Submolecular resolution images have revealed that both the LH2:LH1 ratio, and the architecture of the photosynthetic membrane itself, adapt to light intensity. We investigate the functional implications of structural adaptations in the energy transfer performance in natural in vivo low- and high-light-adapted membrane architectures of Rhodospirillum photometricum . A model is presented to describe excitation migration across the full range of light intensities that cover states from active photosynthesis, where all RCs are available for charge separation, to saturated photosynthesis where all RCs are unavailable. Our study outlines three key findings. First, there is a critical light-energy density, below which the low-light adapted membrane is more efficient at absorbing photons and generating a charge separation at RCs, than the high-light-adapted membrane. Second, connectivity of core complexes is similar in both membranes, suggesting that, despite different growth conditions, a preferred transfer pathway is through core-core contacts. Third, there may be minimal subareas on the membrane which, containing the same LH2:LH1 ratio, behave as minimal functional units as far as excitation transfer efficiency is concerned

Polariton Transitions in Femtosecond Transient Absorption Studies of Ultrastrong Light-Molecule Coupling

Strong light-matter coupling is emerging as a fascinating way to tune optical properties and modify the photophysics of molecular systems. In this work, we studied a molecular chromophore under strong coupling with the optical mode of a Fabry-Perot cavity resonant to the first electronic absorption band. Using femtosecond pump-probe spectroscopy, we investigated the transient response of the cavity-coupled molecules upon photoexcitation resonant to the upper and lower polaritons. We identified an excited state absorption from upper and lower polaritons to a state at the energy of the second cavity mode. Quantum mechanical calculations of the many-molecule energy structure of cavity polaritons suggest assignment of this state as a two-particle polaritonic state with optically allowed transitions from the upper and lower polaritons. We provide new physical insight into the role of two-particle polaritonic states in explaining transient signatures in hybrid light-matter coupling systems consistent with analogous many-body systems