Exciton Transport Efficiency Research Articles

Spatial Patterns of Light-Harvesting Antenna Complex Arrangements Tune the Transfer-to-Trap Efficiency of Excitons in Purple Bacteria.

In photosynthesis, the efficiency with which a photogenerated exciton reaches the reaction center is dictated by chromophore energies and the arrangement of chromophores in the supercomplex. Here, we explore the interplay between the arrangement of light-harvesting antennae and the efficiency of exciton transport in purple bacterial photosynthesis. Using a Miller-Abrahams-based exciton hopping model, we compare different arrangements of light-harvesting proteins on the intracytoplasmic membrane. We find that arrangements with aggregated LH1s have a higher efficiency than arrangements with randomly distributed LH1s in a wide range of physiological light fluences. This effect is robust to the introduction of defects on the intracytoplasmic membrane. Our result explains the absence of species with aggregated LH1 arrangements in low-light niches and the large increase seen in the expression of LH1 dimer complexes in high fluences. We suggest that the effect seen in our study is an adaptive strategy toward solar light fluence across different purple bacterial species.

Engineering couplings for exciton transport using synthetic DNA scaffolds

Summary Control over excitons enables electronic energy to be harnessed and transported for light harvesting and molecular electronics. Such control requires nanoscale precision over the molecular components. Natural light-harvesting systems achieve this precision through sophisticated protein machinery, which is challenging to replicate synthetically. Here, we introduce a DNA-based platform that spatially organizes cyanine chromophores to construct tunable excitonic systems. We synthesized DNA-chromophore nanostructures and characterized them with ensemble ultrafast and single-molecule spectroscopy and structure-based modeling. This synthetic approach facilitated independent control over the coupling among the chromophores and between the chromophores and the environment. We demonstrated that the coupling between the chromophores and the environment could enhance exciton transport efficiency, highlighting the key role of the environment in driving exciton dynamics. Control over excitons, as reported here, offers a path toward the development of designer nanophotonic devices.

The dark side of energy transport along excitonic wires: On-site energy barriers facilitate efficient, vibrationally mediated transport through optically dark subspaces.

We present a novel, counter-intuitive method, based on dark-state protection, for significantly improving exciton transport efficiency through "wires" comprising a chain of molecular sites with an intrinsic energy gradient. Specifically, by introducing "barriers" to the energy landscape at regular intervals along the transport path, we find that undesirable radiative recombination processes are suppressed due to a clear separation of sub-radiant and super-radiant eigenstates in the system. This, in turn, can lead to an improvement in transmitted power by many orders of magnitude, even for very long chains. From there, we analyze the robustness of this phenomenon to changes in both system and environment properties to show that this effect can be beneficial over a range of different thermal and optical environment regimes. Finally, we show that the novel energy landscape presented here may provide a useful foundation for overcoming the short length scales over which exciton diffusion typically occurs in organic photo-voltaics and other nanoscale transport scenarios, thus leading to considerable potential improvements in the efficiency of such devices.

Excited State Relaxation Dynamics of Silicon Nanosheets using Time-dependent Density Functional Tight Binding Theory

By combining time-dependent density functional tight binding (TD-DFTB) calculations for electrons with molecular dynamics simulations, time evolution of excited state relaxation and single electron self-trapping of silicon nanosheets (SinHm) are investigated. We identify the atoms and bonds contributing to the excitations and observe the time evolution of charge density, indicating the migration of exciton from initial position to neighboring bonds. Different temperature 50K and 100K are attempted in the MD simulations, and the temperature is found to affect the electronic localization. Our simulations reveal the formation of exciton trapping and localization on certain bonds upon excitation within the timescale about 200-300fs. In summary, TD-DFTB excited state MD simulations can provide interesting insights into photoreactions and have crucial implications in modulating the exciton transport efficiency in strongly confined low-dimensional systems.

(Invited) Controlling Nanotube-Nanotube Interactions in Carbon Nanotube Networks: Implications for Energy Transport and Harvesting

While the unique chemical and physical structure of semiconducting single-walled carbon nanotubes (s-SWCNTs) were identified decades ago, marking these nanoscale materials as promising candidates for constituents in a variety of optical and electronic applications, the ability to generate high-purity samples has hampered efforts to validate these expectations. The intervening years have played witness to a number of elegant enrichment strategies aimed at extracting tailored semiconducting SWCNT species from the raw soot, from the use of subtly tunable surfactant interactions to the exploitation of specific DNA sequences. In contrast, we employ an enrichment approach based on conjugated polymers, typically derived from the fluorene moiety, since they show great promise with regards to their high selectivity and viability for scalable manufacturing approaches.As alluded to above, these fluorene-based (co-)polymers confer solubility on the s-SWCNT species, allowing for the preparation of highly enriched s-SWCNT dispersions that can be deposited using a variety of solution-processing approaches. Unfortunately, the strong van de Waals forces between the π-electron systems of the polymer and SWCNT that enable the selective extraction of semiconducting SWCNTs with high purity also make removal of the polymer difficult. Since these polymers typically have a wide bandgap they can act as an insulating coating on the surface of the individual SWCNTs within functional networks, inhibiting the transport of energy in the form of excitons and/or charge carriers.Here we demonstrate approaches that allow us to replace the strongly-bound polymers with derivatives that can be removed using simple solution-based chemical strategies, resulting in networks with modified energy transport properties. We show that removal of the polymer results in a significant enhancement of the charge carrier mobility and electrical conductivity in doped s-SWCNT networks. Finally, we extend the approach to samples strongly enriched in a single chiral s-SWCNT species, which allows us to employ transient spectroscopic techniques to probe exciton transport within the s-SWCNT network with high spectral fidelity. We show that the efficiency of exciton transport is subtly dependent on the complex interplay between polymer removal and carbon nanotube bundling. Our studies highlight a methodology by which high-performance s-SWCNT thin films can be prepared and discuss the implications of our findings on the potential to realize their promise for electronic and optoelectronic applications.

Absence of Selection for Quantum Coherence in the Fenna–Matthews–Olson Complex: A Combined Evolutionary and Excitonic Study

We present a study on the evolution of the Fenna–Matthews–Olson bacterial photosynthetic pigment–protein complex. This protein complex functions as an antenna. It transports absorbed photons—excitons—to a reaction center where photosynthetic reactions initiate. The efficiency of exciton transport is therefore fundamental for the photosynthetic bacterium’s survival. We have reconstructed an ancestor of the complex to establish whether coherence in the exciton transport was selected for or optimized over time. We have also investigated the role of optimizing free energy variation upon folding in evolution. We studied whether mutations which connect the ancestor to current day species were stabilizing or destabilizing from a thermodynamic viewpoint. From this study, we established that most of these mutations were thermodynamically neutral. Furthermore, we did not see a large change in exciton transport efficiency or coherence, and thus our results predict that exciton coherence was not specifically selected for.

Coherent Transport and Energy Flow Patterns in Photosynthesis under Incoherent Excitation

Long-lived coherences have been observed in photosynthetic complexes after laser excitation, inspiring new theories regarding the extreme quantum efficiency of photosynthetic energy transfer. Whether coherent (ballistic) transport occurs in nature and whether it improves photosynthetic efficiency remain topics of debate. Here, we use a nonequilibrium Green's function analysis to model exciton transport after excitation from an incoherent source (as opposed to coherent laser excitation). We find that even with an incoherent source, the rate of environmental dephasing strongly affects exciton transport efficiency, suggesting that the relationship between dephasing and efficiency is not an artifact of coherent excitation. The Green's function analysis provides a clear view of both the pattern of excitonic fluxes among chromophores and the multidirectionality of energy transfer that is a feature of coherent transport. We see that even in the presence of an incoherent source, transport occurs by qualitatively different mechanisms as dephasing increases. Our approach can be generalized to complex synthetic systems and may provide a new tool for optimizing synthetic light harvesting materials.

The dependence of exciton transport efficiency on spatial patterns of correlation within the spectral bath

Spatial correlations in spectral bath motions have been proposed to explain long-lived coherence in exciton transport. Systems of interest, ranging from photosynthetic complexes to organic photovoltaics, contain inhomogeneous environments. We consider the possibility that the degree of spatial correlation varies throughout an exciton transport system. We model exciton transport in the Fenna–Matthews–Olson complex (FMO), a photosynthetic light-harvesting complex. Although it remains unclear whether significant spatial correlations exist in FMO, its very high exciton transport efficiency makes it an interesting case for studies of exciton transport. We also simulate a highly symmetric ten-site model system. We use an extension of the environment-assisted quantum transport model to simulate transport, allowing the spatial correlation function to vary throughout the system. We demonstrate both via analysis and via simulation that exciton transport efficiency is most sensitive to changes in correlation between the site coupled to the trap and its neighboring sites. This asymmetry in sensitivity is highly robust and appears irrespective of changes in parameters such as transition dipole orientations and initial conditions. Our results suggest that in the design of exciton transport systems, efforts to increase efficiency by controlling spatial correlation should be focused on the region near the site of exciton trapping.

The role of the environment time scale in light-harvesting efficiency and coherent oscillations

We study the efficiency of exciton transport as a function of the typical reorganization time scale of the environment using the hierarchy of equations of motion. As a model system, we choose the Fenna–Matthews–Olson (FMO) complex. An environment in which the dynamics is not much faster than the system leads to prolonged quantum coherent transport, even at room temperature. We find that this does not make the transport process more efficient for standard FMO parameters, but does increase the efficiency in the case when exciton decay competes with trapping at the reaction center. We furthermore find that initial correlations do not influence population oscillations.

Efficient Exciton Transport between Strongly Quantum-Confined Silicon Quantum Dots

Many-body Green function analysis and first-order perturbation theory are used to quantify the influence of size, surface reconstruction, and surface treatment on exciton transport between small silicon quantum dots. Competing radiative processes are also considered in order to determine how exciton transport efficiency is influenced. The analysis shows that quantum confinement causes small (~1 nm) Si quantum dots to exhibit exciton transport efficiencies far exceeding that of their larger counterparts for the same center-to-center separation. This surprising result offers the prospect of designing assemblies of quantum dots through which excitons can travel for long distances, a game-changing paradigm shift for next-generation solar energy harvesting. We also find that surface reconstruction significantly influences the absorption cross section and leads to a large reduction in both transport rate and efficiency. Further, exciton transport efficiency is higher for hydrogen-passivated dots as compared with those terminated with more electronegative ligands, a result not predicted by Förster theory.

Exciton transport in the photosynthetic unit

In this paper we present a theoretical study of the exciton transport in the photosynthetic unit and attempt to correlate the structural and organizational properties of the unit with the exciton transport efficiency. The transport mechanism is assumed to be of the Forster type. This mechanism is shown to be equivalent to the thermally assisted exciton hopping. The transport equations are solved by the Green's function technique in a more general way than has been presented previously. We thus find it possible to study the effect of the proper R −6 coupling and random orientations of the pigment molecules. The equations are also solved for a low concentration of reaction centres when the conventional random walk picture is not valid. Various models of chlorophyll a and b mixtures are studied and by comparing their different exciton transport properties, an explanation is proposed for several observed features of the primary photochemical process.

The Crystal and Molecular Structure of Ethyl Chlorophyllide a ·2H 2 O and Its Relationship to the Structure and Aggregation of Chlorophyll a

Determination of the crystal structure of ethyl chlorophyllide a.2H(2)O by single crystal x-ray diffraction techniques has provided the first detailed molecular structural data available for a magnesium-containing derivative of chlorophyll. At the same time the aggregation observed in this structure serves as the basis for a model of chlorophyll aggregation in vitro and in vivo. The magnesium atom in ethyl chlorophyllide is displaced 0.4 A from the plane of the chlorin ring in the same direction as the methyl ester substituent. A water molecule occupies the fifth coordination site. A second water molecule is hydrogen bonded to the coordinated water molecule and also to the carbonyl oxygen atom of the methyl ester. Hydrogen bonds between the water molecules and carbonyl oxygen atoms link the chlorophyllide molecules into a two-dimensional aggregate of crosslinked one-dimensional polymers. The relationship of this aggregate to aggregates of chlorophyll both in vitro and in vivo is discussed, as is the efficiency of exciton transport within the polymer.