Optical signatures of quantum delocalization over extended domains in photosynthetic membranes

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 arrays from polarized and unpolarized excitation, and demonstrate that it can be used as a diagnostic tool to determine the coherent coupling among iso-energetic light-harvesting structures. The knowledge of these couplings would then provide further insight into the dynamical properties of transfer, such as facilitating the accurate determination of F\"orster rates.Comment: 4 figures and Supplementary information with 7 figures. To appear in Journal of physical chemistry A, 201

Energy conversion in Purple Bacteria Photosynthesis

The study of how photosynthetic organisms convert light offers insight not only into nature's evolutionary process, but may also give clues as to how best to design and manipulate artificial photosynthetic systems -- and also how far we can drive natural photosynthetic systems beyond normal operating conditions, so that they can harvest energy for us under otherwise extreme conditions. In addition to its interest from a basic scientific perspective, therefore, the goal to develop a deep quantitative understanding of photosynthesis offers the potential payoff of enhancing our current arsenal of alternative energy sources for the future. In the following Chapter, we consider the trade-off between dynamics, structure and function of light harvesting membranes in Rps. Photometricum purple bacteria, as a model to highlight the priorities that arise when photosynthetic organisms adapt to deal with the ever-changing natural environment conditions.Comment: Chapter, to appear in Photosynthesis 2011, INTEC

Light-harvesting in bacteria exploits a critical interplay between transport and trapping dynamics

Light-harvesting bacteria Rhodospirillum Photometricum were recently found to adopt strikingly different architectures depending on illumination conditions. We present analytic and numerical calculations which explain this observation by quantifying a dynamical interplay between excitation transfer kinetics and reaction center cycling. High light-intensity membranes (HLIM) exploit dissipation as a photo-protective mechanism, thereby safeguarding a steady supply of chemical energy, while low light-intensity membranes (LLIM) efficiently process unused illumination intensity by channelling it to open reaction centers. More generally, our analysis elucidates and quantifies the trade-offs in natural network design for solar energy conversion.Comment: 4 pages and 4 figures. Accepted for publication in Physical Review Letters

Memory in the Photon Statistics of Multilevel Quantum Systems

The statistics of photons emitted by single multilevel systems is investigated with emphasis on the nonrenewal characteristics of the photon-arrival times. We consider the correlation between consecutive interphoton times and present closed form expressions for the corresponding multiple moment analysis. Based on the moments a memory measure is proposed which provides an easy way of gaging the non-renewal statistics. Monte-Carlo simulations demonstrate that the experimental verification of non-renewal statistics is feasible.Comment: 5 pages, 3 figure

The nature of the low energy band of the Fenna-Matthews-Olson complex: vibronic signatures

Based entirely upon actual experimental observations on electron-phonon coupling, we develop a theoretical framework to show that the lowest energy band of the Fenna- Matthews-Olson (FMO) complex exhibits observable features due to the quantum nature of the vibrational manifolds present in its chromophores. The study of linear spectra provides us with the basis to understand the dynamical features arising from the vibronic structure in non-linear spectra in a progressive fashion, starting from a microscopic model to finally performing an inhomogenous average. We show that the discreteness of the vibronic structure can be witnessed by probing the diagonal peaks of the non-linear spectra by means of a relative phase shift in the waiting time resolved signal. Moreover, we demonstrate the photon-echo and non-rephasing paths are sensitive to different harmonics in the vibrational manifold when static disorder is taken into account. Supported by analytical and numerical calculations, we show that nondiagonal resonances in the 2D spectra in the waiting time, further capture the discreteness of vibrations through a modulation of the amplitude without any effect in the signal intrinsic frequency. This fact generates a signal that is highly sensitive to correlations in the static disorder of the excitonic energy albeit protected against dephasing due to inhomogeneities of the vibrational ensemble.Comment: 14 pages, 6 figure

Design principles for long-range energy transfer at room temperature

Typical room temperature conditions hinder ballistic long-range transfer of excitations, rendering quantum phenomena unimportant as potential tools for the design of efficient and controllable energy transfer over significant time and length scales. However, it is well-known that many properties of macroscopic systems depend on the quantum properties of minimal repeating units and, as we show here, excitonic energy transfer is no exception. With the support of an exactly solvable model, we are able to show how exciton delocalization and the ensuing formation of dark states within unit cells can be harnessed to support classical propagation over macroscopic distances. We specifically discuss the role of such factors in nano-fabricated arrays of bacterial photosynthetic complexes via extensive simulations. This allows us to resolve the to-date unexplained experimental observation of exciton diffusion lengths in such arrays in terms of an interplay between intra-unit cell thermalization and delocalization, which conspire to create and use robust dark states at room temperature.Comment: Revised presentation and new title, main results unchanged, 11+10 pages, 3+5 figure