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Correlated interaction fluctuations in photosynthetic complexes

The functioning and efficiency of natural photosynthetic complexes is strongly influenced by their embedding in a noisy protein environment, which can even serve to enhance the transport efficiency. Interactions with the environment induce fluctuations of the transition energies of and interactions between the chlorophyll molecules, and due to the fact that different fluctuations will partially be caused by the same environmental factors, correlations between the various fluctuations will occur. We argue that fluctuations of the interactions should in general not be neglected, as these have a considerable impact on population transfer rates, decoherence rates and the efficiency of photosynthetic complexes. Furthermore, while correlations between transition energy fluctuations have been studied, we provide the first quantitative study of the effect of correlations between interaction fluctuations and transition energy fluctuations, and of correlations between the various interaction fluctuations. It is shown that these additional correlations typically lead to changes in interchromophore transfer rates, population oscillations and can lead to a limited enhancement of the light harvesting efficiency

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

Tunable exciton interactions in optical lattices with polar molecules

Rotational excitation of polar molecules trapped in an optical lattice gives rise to rotational excitons. Here we show that non-linear interactions of such excitons can be controlled by an electric field. The exciton--exciton interactions can be tuned to induce exciton pairing, leading to the formation of biexcitons. Tunable non-linear interactions between excitons can be used for many applications ranging from the controlled preparation of entangled quasiparticles to the study of polaron interactions and the effects of non-linear interactions on quantum energy transport in molecular aggregates.Comment: Some typos have been corrected in this versio

Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters

The initial energy transfer in photosynthesis occurs between the light-harvesting pigments and on ultrafast timescales. We analyze the carotenoid to bacteriochlorophyll energy transfer in LH2 Marichromatium purpuratum as well as in an artificial light-harvesting dyad system by using transient grating and two-dimensional electronic spectroscopy with 10 fs time resolution. We find that F\"orster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which leads to a disagreement with both linear absorption and electronic 2D-spectra. We show that a vibronic model, which treats carotenoid vibrations on both electronic ground and excited state as part of the system's Hamiltonian, reproduces all measured quantities. Importantly, the vibronic model presented here can explain the fast energy transfer rates with only moderate coupling constants, which are in agreement with structure based calculations. Counterintuitively, the vibrational levels on the carotenoid electronic ground state play a central role in the excited state population transfer to bacteriochlorophyll as the resonance between the donor-acceptor energy gap and vibrational ground state energies is the physical basis of the ultrafast energy transfer rates in these systems

Constant amplitude and post-overload fatigue crack growth behavior in PM aluminum alloy AA 8009

A recently developed, rapidly solidified, powder metallurgy, dispersion strengthened aluminum alloy, AA 8009, was fatigue tested at room temperature in lab air. Constant amplitude/constant delta kappa and single spike overload conditions were examined. High fatigue crack growth rates and low crack closure levels compared to typical ingot metallurgy aluminum alloys were observed. It was proposed that minimal crack roughness, crack path deflection, and limited slip reversibility, resulting from ultra-fine microstructure, were responsible for the relatively poor da/dN-delta kappa performance of AA 8009 as compared to that of typical IM aluminum alloys

Sensitivities of Low Energy Reactor Neutrino Experiments

The low energy part of the reactor neutrino spectra has not been experimentally measured. Its uncertainties limit the sensitivities in certain reactor neutrino experiments. The origin of these uncertainties are discussed, and the effects on measurements of neutrino interactions with electrons and nuclei are studied. Comparisons are made with existing results. In particular, the discrepancies between previous measurements with Standard Model expectations can be explained by an under-estimation of the low energy reactor neutrino spectra. To optimize the experimental sensitivities, measurements for \nuebar-e cross-sections should focus on events with large ($>$1.5 MeV) recoil energy while those for neutrino magnetic moment searches should be based on events $<$100 keV. The merits and attainable accuracies for neutrino-electron scattering experiments using artificial neutrino sources are discussed.Comment: 25 pages, 9 figure

Long-range energy transport in photosystem II.

We simulate the long-range inter-complex electronic energy transfer in photosystem II-from the antenna complex, via a core complex, to the reaction center-using a non-Markovian (ZOFE) quantum master equation description that allows the electronic coherence involved in the energy transfer to be explicitly included at all length scales. This allows us to identify all locations where coherence is manifested and to further identify the pathways of the energy transfer in the full network of coupled chromophores using a description based on excitation probability currents. We investigate how the energy transfer depends on the initial excitation-localized, coherent initial excitation versus delocalized, incoherent initial excitation-and find that the overall energy transfer is remarkably robust with respect to such strong variations of the initial condition. To explore the importance of vibrationally enhanced transfer and to address the question of optimization in the system parameters, we systematically vary the strength of the coupling between the electronic and the vibrational degrees of freedom. We find that the natural parameters lie in a (broad) region that enables optimal transfer efficiency and that the overall long-range energy transfer on a ns time scale appears to be very robust with respect to variations in the vibronic coupling of up to an order of magnitude. Nevertheless, vibrationally enhanced transfer appears to be crucial to obtain a high transfer efficiency, with the latter falling sharply for couplings outside the optimal range. Comparison of our full quantum simulations to results obtained with a "classical" rate equation based on a modified-Redfield/generalized-Förster description previously used to simulate energy transfer dynamics in the entire photosystem II complex shows good agreement for the overall time scales of excitation energy transport

Modeling 5 Years of Subglacial Lake Activity in the MacAyeal Ice Stream (Antarctica) Catchment Through Assimilation of ICESat Laser Altimetry

Subglacial lakes beneath Antarctica’s fast-moving ice streams are known to undergo ~1km3 volume changes on annual timescales. Focusing on the MacAyeal Ice Stream (MacIS) lake system, we create a simple model for the response of subglacial water distribution to lake discharge events through assimilation of lake volume changes estimated from Ice, Cloud and land Elevation Satellite (ICESat) laser altimetry. We construct a steady-state water transport model in which known subglacial lakes are treated as either sinks or sources depending on the ICESat-derived filling or drainingrates. The modeled volume change rates of five large subglacial lakes in the downstream portion of MacIS are shown to be consistent with observed filling rates if the dynamics of all upstream lakes are considered. However, the variable filling rate of the northernmost lake suggests the presence of an undetected lake of similar size upstream. Overall, we show that, for this fast-flowing ice stream, most subglacial lakes receive \u3e90% of their water from distant distributed sources throughout the catchment, and we confirm that water is transported from regions of net basal melt to regions of net basal freezing. Our study provides a geophysically based means of validating subglacial water models in Antarctica and is a potential way to parameterize subglacial lake discharge events in large-scale ice-sheet models where adequate data are available