Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. Lett. 2019, 10, 15, 4252-4258

Cavity-Modified Exciton Dynamics in Photosynthetic Units

Rocío Sáez-Blázquez
Rocío Sáez-Blázquez
Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, E-28049 Madrid, Spain
More by Rocío Sáez-Blázquez
,
Johannes Feist
Johannes Feist
Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, E-28049 Madrid, Spain
More by Johannes Feist
http://orcid.org/0000-0002-7972-0646
,
Elisabet Romero
Elisabet Romero
Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), E-43007 Tarragona, Spain
More by Elisabet Romero
,
Antonio I. Fernández-Domínguez*
Antonio I. Fernández-Domínguez
Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, E-28049 Madrid, Spain
*E-mail: [email protected]
More by Antonio I. Fernández-Domínguez
http://orcid.org/0000-0002-8082-395X
, and
Francisco J. García-Vidal
Francisco J. García-Vidal
Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, E-28049 Madrid, Spain
Donostia International Physics Center (DIPC), E-20018 Donostia−San Sebastián, Spain
More by Francisco J. García-Vidal
http://orcid.org/0000-0003-4354-0982

Cite this: J. Phys. Chem. Lett. 2019, 10, 15, 4252–4258

Publication Date (Web):July 10, 2019

https://doi.org/10.1021/acs.jpclett.9b01495

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Abstract

Recently, exciton–photon strong coupling has been proposed as a means to control and enhance energy transfer in ensembles of organic molecules. Here, we demonstrate that the exciton dynamics in an archetypal purple bacterial photosynthetic unit, composed of six LH2 antennas surrounding a single LH1 complex, is greatly modified by its interaction with an optical cavity. We develop a Bloch–Redfield master equation approach that accounts for the interplay between the B800 and B850 bacteriochlorophyll molecules within each LH2 antenna, as well as their interactions with the central LH1 complex. Using a realistic parametrization of both the photosynthetic unit and optical cavity, we investigate the formation of polaritons in the system, revealing that these can be tuned to accelerate its exciton dynamics by 3 orders of magnitude. This yields a significant occupation of the LH1 complex, the stage immediately prior to the reaction center, with only a few-femtosecond delay after the initial excitation of the LH2 B800 pigments. Our theoretical findings unveil polaritonic phenomena as a promising route for the characterization, tailoring, and optimization of light-harvesting mechanisms in natural and artificial photosynthetic processes.

Light-harvesting (LH) complexes play a crucial role in the process of photosynthesis. (1,2) They are responsible for collecting, retaining, and funnelling solar energy (3,4) into the reaction centers, where its conversion into chemical energy takes place. (5) These pigment–protein compounds absorb the incident photons and convey the resulting electron–hole excitations through Förster-like, dipole–dipole interactions between neighboring molecules. (6,7) This mechanism is slower than vibrational dephasing in the system, which makes the transport process effectively incoherent. (8,9) Moreover, thanks to the extremely slow nonradiative decay inherent to bacteriochlorophyll molecules, energy transfer in photosynthetic membranes can range micrometric distances and take nanoseconds while having efficiencies approaching 100%. (10,11) A paradigmatic example of phototrophic organisms, widely studied in the literature, is purple bacteria (12,13) such as Rhodopseudomonas acidophila, in whose photosynthetic membranes two different complexes can be identified: (14) LH2, which act mainly as optical antennas, and LH1, which deliver the excitation to the reaction center they enclose. Although the arrangement and distribution of both complexes within the bacterial membrane depend on the ambient and light intensity conditions, there is usually a number of LH2 in the vicinity of every LH1 and attached reaction center. (10,15)

In recent years, much research attention has been focused on exploring the opportunities that the phenomenon of exciton–photon collective strong coupling (16) brings into material science. (17) The coupling between an excitonic platform and the electromagnetic modes supported by an optical cavity gives rise to polaritons, hybrid states whose formation requires that the interaction between light and matter become faster than their respective decay channels. Experimental and theoretical studies demonstrate that the appropriate tailoring of polaritonic characteristics in organic semiconductors and ensembles of organic molecules can yield a large enhancement of the efficiency and spatial range of charge and exciton conductance (18−21) and energy transfer (22−26) in these systems. The coherent and delocalized nature of polaritons plays a crucial role in these phenomena. On one hand, it allows energy transfer within a time scale set by the so-called Rabi frequency (collective coupling strength). (27) On the other hand, it makes the process nonlocal and robust to disorder within a length scale comparable to the optical wavelength. (28)

It has been recently shown that plasmonic nanostructures can modify the optical properties of LH2 antennas. (29−32) Moreover, experimental evidence of collective strong coupling in ensembles of living bacteria has been reported, (33) giving rise even to the concept of living polaritons. (34) In ref (33), a Rabi splitting of around 150 meV has been reported, implying that about 1000 chlorosomes present in green sulfur bacteria are coherently coupled to a cavity photon. In the absence of a cavity, the study of exciton transport in photosynthetic materials has been triggered by the prospect of transferring this knowledge to human-made energy-harvesting structures. In this Letter, we go a step further by assessing the impact that the interaction with an optical cavity has on the efficiency of exciton transport taking place in purple bacterial photosynthetic units (PSUs) formed by several LH complexes. Using Bloch–Redfield theory, (35,36) which allows us to describe vibration-assisted incoherent interactions among bacteriochlorophyll pigments, (6,9) we construct first a quantum master equation describing a single LH2 antenna, involving 27 interacting pigments of three different families (B800, B850a, and B850b). Our model reproduces experimental absorption spectra of freestanding LH2. Next, we consider an archetypal PSU configuration: (10,37) a ring of six LH2 antennas surrounding a single LH1 complex. We extend our master equation to the whole PSU, including incoherent interactions among neighboring pigments within different LH complexes. By introducing pigment–photon coupling terms in the Hamiltonian, we study the formation of polaritons in the system, with special emphasis on the cavity characteristics. We find that strong coupling in realistic cavities can accelerate PSU exciton dynamics by a factor ∼10³, which leads to a considerable population of the LH1 complex within only a few femtoseconds after the initial excitation of LH2 B800 pigments. Our model also reveals how the contribution of the different polaritonic states to this fast population transfer depends on the frequency of the cavity mode and its effective volume (or pigment–photon coupling strength).

Figure 1a sketches the PSU configuration under study: six LH2 antennas arranged around a single LH1 complex. The latter is formed by a number of B875 pigments, (4) which are the final stage of the exciton transfer mechanism we analyze here. Taking this into account, we use a simplified model for the LH1 complex (red circle), valid in the low population regime. We treat it as a single two-level system with transition frequency ω_LH1 = 1.417 eV. (38) Our attention is focused on the LH2 antennas, which we describe in more detail. They are composed of N_LH2 = 27 pigments, distributed in a double-ring structure: (39−41) while nine B800 molecules (blue dots) form one of the rings, the other comprises nine pigment dimers made up of a B850a and a B850b molecule each (light and dark green dots). In our model, the pigments in each LH2 complex are modeled as interacting two-level systems leading to the Hamiltonian

Ĥ_{LH 2} = \sum_{i = 1}^{N_{LH 2}} ω_{i} {σ̂}_{i}^{†} {σ̂}_{i} + \sum_{i, j = 1}^{N_{LH 2}} V_{i j} {{σ̂}_{i}^{†} {σ̂}_{j} + {σ̂}_{j}^{†} {σ̂}_{i}}

(1)

where σ̂_i^† and σ̂_i are the creation and annihilation operators of molecular excitations, and ω_i is their corresponding energies. The parameters in eq 1 are taken from refs (44and45). The freestanding-pigment energies are set to ω_B800 = 1.549 eV and ω_B850a,b = 1.520 eV. The intraring nearest-neighbor (second-nearest-neighbor) couplings are V_B800B800 = 3 meV, V_B850aB850a = 6 meV, V_B850bB850b = 4 meV, and V_B850aB850b = −33(−36) meV. Finally, the inter-ring nearest-neighbor interaction is parametrized by V_B800B850a = −3 meV and V_B800B850b = −1 meV.

Figure 1. (a) Sketch of the PSU considered in this work: 6 LH2 antennas, comprising 9 B800 and 18 B850 molecules each, surrounding a single LH1 complex. The insets show the two-level system exciton model of B-molecules and LH1, which experience both radiative and vibrational decay. (b) Absorption spectrum of a single LH2 complex, including disorder and inhomogeneous broadening. (c) Vibrational spectral density, S(ω), for all LH2 pigments. (d) Exciton population dynamics for the PSU in panel a in an initial state given by the superposition of excited B800 molecules in the six LH2 antennas.

The diagonalization of the Hamiltonian above yields the exciton energies of the LH2 complex. The small inter-ring couplings above translate into excitons strongly localized at B800 or B850(a,b) pigments, with little hybridization among them. (40,41) We check the validity of our model by calculating the absorption spectrum for a single, isolated LH2 antenna. We first compute the transition matrix element of the total dipole moment operator M̂ = ∑_i=1^N_LH2 μ_iσ̂_i^† (μ_B800 = μ_B850 = 6.13 D (46)) for the excitonic eigenstates of eq 1. The absorption spectrum is built as a sum of Lorentzian contributions centered at the excitonic energies and weighted by the square of the corresponding matrix element of the dipole moment operator. Their width was set to 15 meV for B800 and B850 excitons, to take into account the disorder and inhomogeneous broadening inherent to the measurements performed on ensembles of LH2 complexes. (47) The spectrum obtained this way is rendered in Figure 1b, which reproduces the double-peaked absorption profile reported experimentally, (47,48) with maxima around 1.44 eV (860 nm) and 1.55 eV (800 nm).

We use a Bloch–Redfield master equation (6) to describe the vibrational dissipation and incoherent interactions experienced by B800 and B850 molecules. This requires the inclusion of the vibronic spectral density of the pigments, S(ω). Figure 1c plots S(ω) in our calculations (the same for B800 and B850 molecules), parametrized using the Franck–Condon factors in ref (42) and a thermal line broadening in agreement with ref (43). Lindblad terms of the form $\frac{γ_{0}}{2} L_{{σ̂}_{i}} [ρ̂] = \frac{γ_{0}}{2} [2 {σ̂}_{i} {ρ̂ σ̂}_{i}^{†} - {ρ {σ̂}_{i}^{†} {σ̂}_{i}}]$ , acting on all pigment annihilation operators, are also included in the master equation, weighted by a decay rate γ₀ = 1 μeV, which reflects the ∼1 ns lifetime of all the molecules in the LH2 complex. (4) Note that the exciton widths introduced in the cross-section calculations are ∼10⁴ times larger than this value.

The master equation for the whole PSU is built next. It is composed by blocks, corresponding to the six LH2 antennas and the central LH1 complex, only connected through Lindblad terms of the form $\frac{γ_{B 850 LH 1}}{2} L_{{σ̂}_{LH 1}^{†} {σ̂}_{n, 1}} [ρ̂]$ . These act on the product of the annihilation operator for the B850 molecule (which we label as i = 1) in the nth LH2 antenna that is located next to the LH1 complex, and the LH1 creation operator. The associated decay rate is set to γ_B850LH1 = 2 meV, which yields LH2–LH1 transition rates in agreement with experiments. (37) This is shown in Figure 1d, which plots the population transients for a freestanding PSU. The initial state corresponds to the coherent superposition of excitations in all the B800 pigments, which mimics an experimental setup in which the PSU is pumped by an ultrashort laser pulse centered around 800 nm. We can observe that this state (blue line) decays within ∼3 ps, feeding population into the LH2 B850 molecules (green line). These in turn carry the excitation to the LH1 complex (red line), whose population grows within a ∼20 ps time scale after the initial excitation. The time interval in Figure 1d is much shorter than γ₀^–1, and the ground state (shown in black line) is negligibly populated in the whole exciton transfer process. Note that we have taken γ₁ = 0, see Figure 1a, to avoid the decay of the LH1 excitations into the ground state.

To analyze the effect of strong coupling in the PSU exciton dynamics, we add new terms to the freestanding PSU Hamiltonian, describing the coherent interactions between pigments and cavity photons

Ĥ = ω_{C} â^{†} â + ω_{LH 1} {σ̂}_{LH 1}^{†} {σ̂}_{LH 1} + \sum_{n = 1}^{6} Ĥ_{LH 2, n} + g_{0} [\sum_{n = 1}^{6} \sum_{i = 1}^{N_{LH 2}} ({σ̂}_{n, i}^{†} â + {σ̂}_{n, i} â^{†}) + η ({σ̂}_{LH 1}^{†} â + {σ̂}_{LH 1} â^{†})]

(2)

where ω_C is the cavity frequency, â^† and â are the creation and annihilation operators for the cavity mode, g₀ is the photon coupling strength to all LH2 pigments, and η = 3.8 is the dipole moment of the LH1 complex normalized to μ_B800. (4) There, Ĥ_LH2,n is the Hamiltonian for the nth LH2 antenna (see eq 1). As a result of the interaction between molecules and cavity and the symmetry of the structure, only four hybrid light–matter states arise when entering into the strong-coupling regime, in addition to the set of the so-called dark states. These states are linear combinations of electronic excitations within the LH1 and LH2 complexes that do not couple to the cavity mode. Figure 2a renders the four polaritonic frequencies, as well as those corresponding to the set of dark states, versus the cavity frequency. They are obtained directly from the diagonalization of eq 2. Color lines plot the dispersion of the lower (LP, yellow), middle (MP₁ and MP₂, green and blue), and upper (UP, violet) polariton bands. Note that, certainly, the PSU dark states (gray lines) remain uncoupled to the cavity field. In our calculations, we have taken g₀ = 9 meV. Using

g_{0} = μ_{B 800} \sqrt{ω_{C} / 2 ϵ_{0} V_{eff}}

, (49) this value corresponds to V_eff = (15 nm)³ at ω_C = 1.6 eV. This is attainable not only in plasmonic but also in state-of-the-art dielectric cavities. (50)

Figure 2. (a) Energies of the lower (LP, yellow), middle (MP₁, green, and MP₂, blue), and upper (UP, violet) polaritons versus the cavity frequency, ω_C, and for g₀ = 9 meV. (b) Coefficients representing the cavity (yellow), LH1 (red), B800 (blue), and B850 (green) content of the four polaritons in panel a as a function of ω_C.

Figure 2b shows, from left to right, the square of the Hopfield coefficients for the LP, MP₁, MP₂, and UP as a function of the cavity frequency. Calculated as |⟨i|α⟩|², where α(i) labels the polaritonic (exciton and cavity) states, they weight the cavity (yellow), LH1 (red), B800 (blue), and B850 (green) contents of each polariton. We can observe that the polariton character can be greatly modified through ω_C. Note that only the LP and UP present a substantial cavity content, but they do it at low and high cavity frequencies, respectively. Far from these spectral regions, LP (UP) virtually overlaps with the LH1 (B800) states. On the contrary, the MPs present a moderate cavity component but combine excitonic contents corresponding to all PSU pigments. We anticipate that the hybrid character of these states (especially evident for MP₂ at ω_C ≃ 1.45 eV, where B800 and B850 coefficients become similar) will play a fundamental role in the polariton-assisted population transfer in the PSU. (26)

Having studied the formation of polaritons in the hybrid cavity–PSU system, and the tuning of their characteristics through the cavity frequency, we investigate next its population dynamics. To do so, we extend the master equation for the freestanding PSU by the inclusion of the Hamiltonian in eq 2, and by adding a Lindblad term describing the cavity losses. We set the cavity decay rate to γ_C = 13 μeV, which corresponds to a lifetime of 50 ps and a quality factor Q = ω_C/2γ_C ≃ 6 × 10⁴, parameters similar to those recently reported in deeply subwavelength dielectric cavities. (50) Similarly to Figure 1d and to perform a meaningful comparison against the freestanding PSU, we set the initial state as the coherent superposition of equally excited B800 molecules, and choose ω_C = 1.6 eV and g₀ = 9 meV. Figure 2b shows that the LP is composed of LH1 excitations mostly at this cavity frequency, which allows us to set the final stage of the polariton-assisted energy transfer mechanism at the LH1 complex.

Figure 3 displays the comparison between the population dynamics for the PSU in isolation (dashed lines) and interacting with the cavity described above (solid lines). Figure 3a shows that exciton–photon strong coupling in the PSU gives rise to an extremely fast occupation of the LH1 complex, which acquires a significant population (∼10%) within only a 20 fs delay. In absence of the cavity, the LH1 population is negligible in this time scale and becomes comparable only after a few ps (see Figure 1d). This is the main result in this Letter, the polariton-assisted reduction in population transfer times taking place in PSUs by 3 orders of magnitude. The thin solid line renders the LH1 population when the cavity, instead of the B800 pigments, is initially excited, proving that this phenomenon also takes place in this configuration.

Figure 3. Exciton dynamics for the PSU in Figure 1. (a) LH1 population versus time after the initial excitation of the B800 molecules for the PSU isolated (dashed line) and coupled to an optical cavity with ω_C = 1.6 eV and g₀ = 9 meV (solid line). The thin solid line plots the LH1 population for an initial excitation of the cavity mode. (b) Temporal evolution of the ground state (black), B800 (blue), and B850 (green) populations with (solid line) and without (dashed line) cavity. The cavity population is shown in the yellow solid line. The differences between populations have been shaded in all cases to highlight the effect of strong coupling.

Figure 3b plots the population transients for B800 (blue) and B850 (green) excitons, both exhibiting more regular Rabi oscillations than the LH1. These are especially apparent in the B800 case. Its occupation remains constant and close to unity for the freestanding PSU, but the occurrence of strong coupling gives rise to a coherent energy exchange that feeds population into the other excitonic and cavity (yellow line) states. Black lines correspond to the ground state, whose population is larger in the strong-coupling regime. This is a consequence of the short lifetime of the cavity relative to the PSU pigments (γ_C ∼ γ₀/20). This loss channel can be mitigated by using nanocavities with higher-quality factors. Note that all the time traces in Figure 3 were calculated assuming the same coupling strength for all the B800 and B850 pigments in the PSU (see eq 2). Importantly, our findings hold beyond this approximation, as long as the PSU–cavity Rabi frequency remains the same as in the uniform description. (26)

Up to this point, we have demonstrated that the exciton dynamics in PSUs is greatly modified due to the interaction with a particular optical cavity configuration. We have also shown that this phenomenon is mediated by the polaritons that emerge in the system, whose character varies strongly with the frequency of the cavity. In the following, we shed insights into both findings by investigating the dependence of the B800-to-LH1 population transfer and the polaritonic content of B800 and LH1 excitations on the two parameters set by the optical cavity: ω_C and g₀. Figure 4a displays a contour plot of the LH1 population averaged over the first 300 fs after the excitation of the B800 molecules (the time span in Figure 3). Note that the temporal averaging naturally removes peak effects related to the irregular Rabi oscillations apparent in Figure 3a. We can observe that, by increasing the exciton–photon coupling (reducing the cavity mode volume), the LH1 population grows, although not in a purely monotonic fashion (small oscillations are apparent). On the contrary, the dependence on ω_C is much weaker. This is a surprising result, given the strong dependence of the Hopfield coefficients, and therefore the polariton character, on the cavity frequency shown in Figure 2b.

Figure 4. (a) LH1 population averaged over the first 300 fs after the excitation of the LH2 B800 pigments versus cavity frequency and photon–exciton coupling strength. Color solid lines render contours of the magnitude ∑_αχ_α (see panel below). (b) Polariton component of B800 and LH1 excitations, χ_α = |⟨α|LH1⟩|² |⟨α|B800⟩|², with α = LP, MP₁, MP₂, and UP. (c) LH1 population 40 ps after the initial excitation of the system as a function of ω_C and g₀.

Figure 4b plots the combination of content of B800 and LH1 excitations on the various polaritons α, χ_α = |⟨α|LH1⟩|² |⟨α|B800⟩|², as a function of the cavity frequency and coupling strength. We can observe that, as expected, χ_α grows with g₀ in all cases, as the light–matter hybridization increases with this parameter. However, the B800 and LH1 projections over the different polaritons vary much with ω_C. For large couplings (g₀ > 10 meV), χ_LP dominates LH1 excitations for blue-detuned cavities, whereas χ_MP₂ and χ_UP are the largest contributions for red-detuned ones. On the other hand, for modest couplings (g₀ ≲ 10 meV), χ_LP and χ_MP₁ are largest for red-detuned cavities, while χ_MP₂ and χ_UP present a maximum within the spectral window between 1.5 and 1.6 eV. These panels indicate that the interplay among the different polaritons plays a crucial role in the fast B800-to-LH1 population transfer in PSUs. This conclusion is supported by the contour lines in Figure 4a, which render ∑_αχ_α, showing that this magnitude presents the same dependence on ω_C and g₀ as the LH1 averaged population.

Finally, Figure 4c displays the LH1 population evaluated 40 ps after the initial B800 excitation. We can observe that, for the cavity parameters in Figure 3 (which maximize its population at short times), the LH1 occupation at long times is ∼50%, lower than for the freestanding PSU (see Figure 1d). The origin of this low LH1 occupation at long times can be found in Figure 2b. Note that the Hopfield coefficients for the LP reveal that the lowest energy level in the hybrid PSU–cavity system has only a 50% content on the LH1 state at ω_C = 1.6 eV. However, the comparison between Figures 4a and 4c proves that a compromise between populations at short and long times can be achieved at large coupling strengths (g₀ > 10 meV) and intermediate cavity frequencies (ω_C ≃ 1.5 eV).

To conclude, we have investigated exciton–photon strong coupling in an archetypal purple bacterial photosynthetic unit, comprising six LH2 antennas surrounding a single LH1 complex. We have developed a master equation combining Bloch–Redfield and Lindblad approaches to describe the vibration-assisted incoherent interactions among the B800, B850, and LH1 excitons, as well as their coherent coupling to the electromagnetic mode supported by an optical cavity. Using this tool, we have explored the formation of polaritons in the system, analyzing their dependence on the cavity configuration. We have revealed that these hybrid light–matter states yield a 3 orders of magnitude reduction in the B800-to-LH1 population transfer times, leading to a significant LH1 occupation in a few-femtosecond time scale. We believe that our theoretical findings demonstrate the potential of exciton–photon strong coupling not only for the characterization of light-harvesting phenomena in natural photosynthesis but also as a means for the design and optimization of artificial photosynthetic systems.

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Corresponding Author
- Antonio I. Fernández-Domínguez - Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, E-28049 Madrid, Spain; http://orcid.org/0000-0002-8082-395X; Email: [email protected]
Authors
- Rocío Sáez-Blázquez - Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, E-28049 Madrid, Spain
- Johannes Feist - Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, E-28049 Madrid, Spain; http://orcid.org/0000-0002-7972-0646
- Elisabet Romero - Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), E-43007 Tarragona, Spain
- Francisco J. García-Vidal - Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, E-28049 Madrid, Spain; Donostia International Physics Center (DIPC), E-20018 Donostia−San Sebastián, Spain; http://orcid.org/0000-0003-4354-0982; Email: [email protected]
Notes
The authors declare no competing financial interest.

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This work has been funded by the European Research Council under Grant Agreements ERC-2011-AdG 290981 and ERC-2016-STG-714870, the EU Seventh Framework Programme (FP7-PEOPLE-2013-CIG-630996), and the Spanish MINECO under contracts MAT2014-53432-C5-5-R and FIS2015-64951-R, and through the “Marı́a de Maeztu” programme for Units of Excellence in R&D (MDM-2014-0377), as well as through two Ramon y Cajal grants (J.F. and A.I.F.-D.). We also acknowledge support by the QuantERA program of the European Commission with funding by the Spanish AEI through project PCI2018-093145. E.R. thanks the ICIQ Foundation for the Starting Career Programme and the Generalitat de Catalunya for the CERCA Programme.

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A review. Modern civilization is dependent upon fossil fuels, a nonrenewable energy source originally provided by the storage of solar energy. Fossil-fuel dependence has severe consequences, including energy security issues and greenhouse gas emissions. The consequences of fossil-fuel dependence could be avoided by fuel-producing artificial systems that mimic natural photosynthesis, directly converting solar energy to fuel. This review describes the three key components of solar energy conversion in photosynthesis: light harvesting, charge sepn., and catalysis. These processes are compared in natural and in artificial systems. Such a comparison can assist in understanding the general principles of photosynthesis and in developing working devices, including photoelectrochem. cells, for solar energy conversion.
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Mirkovic, T.; Ostroumov, E.; Anna, J. M.; van Grondelle, R.; Govindjee; Scholes, G. D. Light absorption and energy transfer in the antenna complexes of photosynthetic organisms. Chem. Rev. 2017, 117, 249– 293, DOI: 10.1021/acs.chemrev.6b00002
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Light absorption and energy transfer in the antenna complexes of photosynthetic organisms
Mirkovic, Tihana; Ostroumov, Evgeny E.; Anna, Jessica M.; van Grondelle, Rienk; Govindjee; Scholes, Gregory D.
Chemical Reviews (Washington, DC, United States) (2017), 117 (2), 249-293CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
A review. The process of photosynthesis is initiated by the capture of sunlight by a network of light-absorbing mols. (chromophores), which are also responsible for the subsequent funneling of the excitation energy to the reaction centers. Through evolution, genetic drift, and speciation, photosynthetic organisms have discovered many solns. for light harvesting. In this review, we describe the underlying photophys. principles by which this energy is absorbed, as well as the mechanisms of electronic excitation energy transfer (EET). First, optical properties of the individual pigment chromophores present in light-harvesting antenna complexes are introduced, and then we examine the collective behavior of pigment-pigment and pigment-protein interactions. The description of energy transfer, in particular multichromophoric antenna structures, is shown to vary depending on the spatial and energetic landscape, which dictates the relative coupling strength between constituent pigment mols. In the latter half of the article, we focus on the light-harvesting complexes of purple bacteria as a model to illustrate the present understanding of the synergetic effects leading to EET optimization of light-harvesting antenna systems while exploring the structure and function of the integral chromophores. We end this review with a brief overview of the energy-transfer dynamics and pathways in the light-harvesting antennas of various photosynthetic organisms.
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Romero, E.; Novoderezhkin, V. I.; van Grondelle, R. Quantum design of photosynthesis for bio-inspired solar-energy conversion. Nature 2017, 543, 355– 365, DOI: 10.1038/nature22012
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Quantum design of photosynthesis for bio-inspired solar-energy conversion
Romero, Elisabet; Novoderezhkin, Vladimir I.; van Grondelle, Rienk
Nature (London, United Kingdom) (2017), 543 (7645), 355-365CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
Photosynthesis is the natural process that converts solar photons into energy-rich products that are needed to drive the biochem. of life. Two ultrafast processes form the basis of photosynthesis: excitation energy transfer and charge sepn. Under optimal conditions, every photon that is absorbed is used by the photosynthetic organism. Fundamental quantum mechanics phenomena, including delocalization, underlie the speed, efficiency and directionality of the charge-sepn. process. At least four design principles are active in natural photosynthesis, and these can be applied practically to stimulate the development of bio-inspired, human-made energy conversion systems.
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Novoderezhkin, V. I.; van Grondelle, R. Physical origins and models of energy transfer in photosynthetic light-harvesting. Phys. Chem. Chem. Phys. 2010, 12, 7352– 7365, DOI: 10.1039/c003025b
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Physical origins and models of energy transfer in photosynthetic light-harvesting
Novoderezhkin, Vladimir I.; van Grondelle, Rienk
Physical Chemistry Chemical Physics (2010), 12 (27), 7352-7365CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
A quant. comparison of different energy transfer theories, i.e. modified Redfield, std. and generalized Foerster theories, as well as combined Redfield-Foerster approach, is performed. Phys. limitations of these approaches are illustrated and crit. values of the key parameters indicating their validity are found. The spectra and dynamics in two photosynthetic antenna complexes, in phycoerythrin 545 from cryptophyte algae and in trimeric LHCII complex from higher plants, were modeled at a quant. level. These two examples show how the structural organization dets. a directed energy transfer and how equilibration within antenna subunits and migration between subunits are superimposed.
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Ye, J.; Sun, K.; Zhao, Y.; Yu, Y.; Lee, C. K.; Cao, J. Excitonic energy transfer in light-harvesting complexes in purple bacteria. J. Chem. Phys. 2012, 136, 245104, DOI: 10.1063/1.4729786
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Excitonic energy transfer in light-harvesting complexes in purple bacteria
Ye, Jun; Sun, Kewei; Zhao, Yang; Yu, Yunjin; Kong Lee, Chee; Cao, Jianshu
Journal of Chemical Physics (2012), 136 (24), 245104/1-245104/17CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
Two distinct approaches, the Frenkel-Dirac time-dependent variation and the Haken-Strobl model, are adopted to study energy transfer dynamics in single-ring and double-ring light-harvesting (LH) systems in purple bacteria. It is found that the inclusion of long-range dipolar interactions in the two methods results in significant increase in intra- or inter-ring exciton transfer efficiency. The dependence of exciton transfer efficiency on trapping positions on single rings of LH2 (B850) and LH1 is similar to that in toy models with nearest-neighbor coupling only. However, owing to the symmetry breaking caused by the dimerization of BChls and dipolar couplings, such dependence has been largely suppressed. In the studies of coupled-ring systems, both methods reveal an interesting role of dipolar interactions in increasing energy transfer efficiency by introducing multiple intra/inter-ring transfer paths. Importantly, the time scale (4 ps) of inter-ring exciton transfer obtained from polaron dynamics is in good agreement with previous studies. In a double-ring LH2 system, non-nearest neighbor interactions can induce symmetry breaking, which leads to global and local min. of the av. trapping time in the presence of a non-zero dephasing rate, suggesting that environment dephasing helps preserve quantum coherent energy transfer when the perfect circular symmetry in the hypothetic system is broken. This study reveals that dipolar coupling between chromophores may play an important role in the high energy transfer efficiency in the LH systems of purple bacteria and many other natural photosynthetic systems. (c) 2012 American Institute of Physics.
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Cheng, Y.-C.; Fleming, G. R. Dynamics of light harvesting in photosynthesis. Annu. Rev. Phys. Chem. 2009, 60, 241– 62, DOI: 10.1146/annurev.physchem.040808.090259
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Dynamics of light harvesting in photosynthesis
Cheng, Yuan-Chung; Fleming, Graham R.
Annual Review of Physical Chemistry (2009), 60 (), 241-262CODEN: ARPLAP; ISSN:0066-426X. (Annual Reviews Inc.)
A review of recent theor. and exptl. advances in the elucidation of the dynamics of light harvesting in photosynthesis, focusing on recent theor. developments in structure-based modeling of electronic excitations in photosynthetic complexes and critically examg. theor. models for excitation energy transfer. Two-dimensional electronic spectroscopy and its application to the study of photosynthetic complexes, in particular the Fenna-Matthews-Olson complex from green sulfur bacteria are briefly described. This review emphasizes recent exptl. observations of long-lasting quantum coherence in photosynthetic systems and the implications of quantum coherence in natural photosynthesis.
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Fassioli, F.; Dinshaw, R.; Arpin, P. C.; Scholes, G. D. Photosynthetic light harvesting: excitons and coherence. J. R. Soc., Interface 2014, 11, 20130901, DOI: 10.1098/rsif.2013.0901
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Photosynthetic light harvesting: excitons and coherence
Fassioli, Francesca; Dinshaw, Rayomond; Arpin, Paul C.; Scholes, Gregory D.
Journal of the Royal Society, Interface (2014), 11 (92), 20130901/1-20130901/22CODEN: JRSICU; ISSN:1742-5689. (Royal Society)
A review. Photosynthesis begins with light harvesting, where specialized pigment-protein complexes transform sunlight into electronic excitations delivered to reaction centers to initiate charge sepn. There is evidence that quantum coherence between electronic excited states plays a role in energy transfer. In this review, we discuss how quantum coherence manifests in photosynthetic light harvesting and its implications. We begin by examg. the concept of an exciton, an excited electronic state delocalized over several spatially sepd. mols., which is the most widely available signature of quantum coherence in light harvesting. We then discuss recent results concerning the possibility that quantum coherence between electronically excited states of donors and acceptors may give rise to a quantum coherent evolution of excitations, modifying the traditional incoherent picture of energy transfer. Key to this (partially) coherent energy transfer appears to be the structure of the environment, in particular the participation of non-equil. vibrational modes. We discuss the open questions and controversies regarding quantum coherent energy transfer and how these can be addressed using new exptl. techniques.
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Caycedo-Soler, F.; Rodríguez, F. J.; Quiroga, L.; Johnson, N. F. Light-harvesting mechanism of bacteria exploits a critical interplay between the dynamics of transport and trapping. Phys. Rev. Lett. 2010, 104, 158302, DOI: 10.1103/PhysRevLett.104.158302
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Light-Harvesting Mechanism of Bacteria Exploits a Critical Interplay between the Dynamics of Transport and Trapping
Caycedo-Soler, Felipe; Rodriguez, Ferney J.; Quiroga, Luis; Johnson, Neil F.
Physical Review Letters (2010), 104 (15), 158302/1-158302/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
Light-harvesting bacteria Rhodospirillum photometricum were recently found to adopt strikingly different architectures depending on illumination conditions. We present analytic and numerical calcns. which explain this observation by quantifying a dynamical interplay between excitation transfer kinetics and reaction center cycling. High light-intensity membranes exploit dissipation as a photoprotective mechanism, thereby safeguarding a steady supply of chem. energy, while low light-intensity membranes efficiently process unused illumination intensity by channeling it to open reaction centers. More generally, our anal. elucidates and quantifies the trade-offs in natural network design for solar energy conversion.
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Timpmann, K.; Chenchiliyan, M.; Jalviste, E.; Timney, J. A.; Hunter, C. N.; Freiberg, A. Efficiency of light harvesting in a photosynthetic bacterium adapted to different levels of light. Biochim. Biophys. Acta, Bioenerg. 2014, 1837, 1835– 1846, DOI: 10.1016/j.bbabio.2014.06.007
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Efficiency of light harvesting in a photosynthetic bacterium adapted to different levels of light
Timpmann, Kou; Chenchiliyan, Manoop; Jalviste, Erko; Timney, John A.; Hunter, C. Neil; Freiberg, Arvi
Biochimica et Biophysica Acta, Bioenergetics (2014), 1837 (10), 1835-1846CODEN: BBBEB4; ISSN:0005-2728. (Elsevier B. V.)
In this study, we use the photosynthetic purple bacterium Rhodobacter sphaeroides to find out how the acclimation of photosynthetic app. to growth conditions influences the rates of energy migration toward the reaction center traps and the efficiency of charge sepn. at the reaction centers. To answer these questions we measured the spectral and picosecond kinetic fluorescence responses as a function of excitation intensity in membranes prepd. from cells grown under different illumination conditions. A kinetic model anal. yielded the microscopic rate consts. that characterize the energy transfer and trapping inside the photosynthetic unit as well as the dependence of exciton trapping efficiency on the ratio of the peripheral LH2 and core LH1 antenna complexes, and on the wavelength of the excitation light. A high quantum efficiency of trapping over 80% was obsd. in most cases, which decreased toward shorter excitation wavelengths within the near IR absorption band. At a fixed excitation wavelength the efficiency declines with the LH2/LH1 ratio. From the perspective of the ecol. habitat of the bacteria the higher population of peripheral antenna facilitates growth under dim light even though the energy trapping is slower in low light adapted membranes. The similar values for the trapping efficiencies in all samples imply a robust photosynthetic app. that functions effectively at a variety of light intensities.
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Hunter, C. N.; Daldal, F.; Thurnauer, M. C.; Beatty, J. T. The purple phototrophic bacteria; Springer: Netherlands, 2009.
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Cogdell, R. J.; Gall, A.; Köhler, J. The architecture and function of the light-harvesting apparatus of purple bacteria: from single molecules to in vivomembrane. Q. Rev. Biophys. 2006, 39, 227– 324, DOI: 10.1017/S0033583506004434
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The architecture and function of the light-harvesting apparatus of purple bacteria: from single molecules to in vivo membranes
Cogdell, Richard J.; Gall, Andrew; Koehler, Juergen
Quarterly Reviews of Biophysics (2006), 39 (3), 227-324CODEN: QURBAW; ISSN:0033-5835. (Cambridge University Press)
A review. This review describes the structures of the two major integral membrane pigment complexes, the RC-LH1 'core' and LH2 complexes, which together make up the light-harvesting system present in typical purple photosynthetic bacteria. The antenna complexes serve to absorb incident solar radiation and to transfer it to the reaction centers, where it is used to 'power' the photosynthetic redox reaction and ultimately leads to the synthesis of ATP. Our current understanding of the biosynthesis and assembly of the LH and RC complexes is described, with special emphasis on the roles of the newly described bacteriophytochromes. Using both the structural information and that obtained from a wide variety of biophys. techniques, the details of each of the different energy-transfer reactions that occur, between the absorption of a photon and the charge sepn. in the RC, are described. Special emphasis is given to show how the use of single-mol. spectroscopy has provided a more detailed understanding of the mol. mechanisms involved in the energy-transfer processes. We have tried, with the help of an Appendix, to make the details of the quantum mechanics that are required to appreciate these mol. mechanisms, accessible to math. illiterate biologists. The elegance of the purple bacterial light-harvesting system lies in the way in which it has cleverly exploited quantum mechanics.
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Nagarajan, V.; Parson, W. W. Excitation energy transfer between the B850 and B875 antenna complexes of Rhodobacter Sphaeroides. Biochemistry 1997, 36, 2300– 2306, DOI: 10.1021/bi962534b
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Excitation energy transfer between the B850 and B875 antenna complexes of Rhodobacter sphaeroides
Nagarajan, V.; Parson, W. W.
Biochemistry (1997), 36 (8), 2300-2306CODEN: BICHAW; ISSN:0006-2960. (American Chemical Society)
Energy transfer between the B850 (LH2) and B875 (LH1) antenna complexes of a mutant strain of Rhodobacter sphaeroides lacking reaction centers is investigated by femtosecond pump-probe spectroscopy at room temp. Measurements are made at wavelengths between 810 and 910 nm at times extending to 200 ps after selective excitation of either B850 or B875. Assignments of the spectroscopic signals to the two types of antenna complex are made on the basis of measurements in strains that lack either LH1 or LH2 in addn. to reaction centers. Energy transfer from excited B850 to B875 proceeds with two time consts., 4.6 ± 0.3 and 26.3 ± 1.0 ps, but a significant fraction of the excitations remain in B850 for considerably longer times. The fast step is interpreted as hopping of energy to LH1 from an assocd. LH2 complex; the slower steps are investigated as migration of excitations in the LH2 pool preceding transfer to LH1. Transfer of excitations from B875 to B850 could not be detected, possibly suggesting that the av. no. of LH2 complexes in contact with each LH1 is small.
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Cleary, L.; Chen, H.; Chuang, C.; Silbey, R. J.; Cao, J. Optimal fold symmetry of LH2 rings on a photosynthetic membrane. Proc. Natl. Acad. Sci. U. S. A. 2013, 110, 8537– 8542, DOI: 10.1073/pnas.1218270110
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Optimal fold symmetry of LH2 rings on a photosynthetic membrane
Cleary, Liam; Chen, Hang; Chuang, Chern; Silbey, Robert J.; Cao, Jianshu
Proceedings of the National Academy of Sciences of the United States of America (2013), 110 (21), 8537-8542, S8537/1-S8537/5CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
An intriguing observation of photosynthetic light-harvesting systems is the N-fold symmetry of light-harvesting complex 2 (LH2) of purple bacteria. We calc. the optimal rotational configuration of N-fold rings on a hexagonal lattice and establish two related mechanisms for the promotion of max. excitation energy transfer (EET). (i) For certain fold nos., there exist optimal basis cells with rotational symmetry, extendable to the entire lattice for the global optimization of the EET network. (ii) The type of basis cell can reduce or remove the frustration of EET rates across the photosynthetic network. We find that the existence of a basis cell and its type are directly related to the no. of matching points S between the fold symmetry and the hexagonal lattice. The two complementary mechanisms provide selection criteria for the fold no. and identify groups of consecutive nos. Remarkably, one such group consists of the naturally occurring 8-, 9-, and 10-fold rings. By considering the inter-ring distance and EET rate, we demonstrate that this group can achieve minimal rotational sensitivity in addn. to an optimal packing d., achieving robust and efficient EET. This corroborates our findings i and ii and, through their direct relation to 5, suggests the design principle of matching the internal symmetry with the lattice order.
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Lidzey, D. G.; Bradley, D. D. C.; Skolnick, M. S.; Virgili, T.; Walker, S.; Whittaker, D. M. Strong exciton–photon coupling in an organic semiconductor microcavity. Nature 1998, 395, 53– 55, DOI: 10.1038/25692
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Strong exciton-photon coupling in an organic semiconductor microcavity
Lidzey, D. G.; Gradley, D. D. C.; Skolnick, M. S.; Virgili, T.; Walker, S.; Whittaker, D. M.
Nature (London) (1998), 395 (6697), 53-55CODEN: NATUAS; ISSN:0028-0836. (Macmillan Magazines)
The modification and control of exciton-photon interactions in semiconductors is of both fundamental and practical interest, being of direct relevance to the design of improved light-emitting diodes, photodetectors and lasers. In a semiconductor microcavity, the confined electromagnetic field modifies the optical transitions of the material. Two distinct types of interaction are possible: weak and strong coupling. In the former perturbative regime, the spectral and spatial distribution of the emission is modified but exciton dynamics are little altered. In the latter case, however, mixing of exciton and photon states occurs leading to strongly modified dynamics. Both types of effect were obsd. in planar microcavity structures in inorg. semiconductor quantum wells and bulk layers. But org. semiconductor microcavities were studied only in the weak-coupling regime. An org. semiconductor microcavity that operates in the strong-coupling regime is reported. Characteristic mixing is seen of the exciton and photon modes (anti-crossing), and a room-temp. vacuum Rabi splitting (an indicator of interaction strength) that is an order of magnitude larger than the previously reported highest values for inorg. semiconductors. The results may lead to new structures and device concepts incorporating hybrid states of org. and inorg. excitons, and suggest that polariton lasing may be possible.
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Ebbesen, T. W. Hybrid light-matter states in molecular and material science. Acc. Chem. Res. 2016, 49, 2403– 2412, DOI: 10.1021/acs.accounts.6b00295
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Hybrid Light-Matter States in a Molecular and Material Science Perspective
Ebbesen, Thomas W.
Accounts of Chemical Research (2016), 49 (11), 2403-2412CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
A review. The notion that light and matter states can be hybridized the way s and p orbitals are mixed is a concept that is not familiar to most chemists and material scientists. Yet it has much potential for mol. and material sciences that is just beginning to be explored. For instance, it has already been demonstrated that the rate and yield of chem. reactions can be modified and that the cond. of org. semiconductors and nonradiative energy transfer can be enhanced through the hybridization of electronic transitions. The hybridization is not limited to electronic transitions; it can be applied for instance to vibrational transitions to selectively perturb a given bond, opening new possibilities to change the chem. reactivity landscape and to use it as a tool in (bio)mol. science and spectroscopy. Such results are not only the consequence of the new eigenstates and energies generated by the hybridization. The hybrid light-matter states also have unusual properties: they can be delocalized over a very large no. of mols. (up to ca. 105), and they become dispersive or momentum-sensitive. Importantly, the hybridization occurs even in the absence of light because it is the zero-point energies of the mol. and optical transitions that generate the new light-matter states. The present work is not a review but rather an Account from the author's point of view that first introduces the reader to the underlying concepts and details of the features of hybrid light-matter states. It is shown that light-matter hybridization is quite easy to achieve: all that is needed is to place mols. or a material in a resonant optical cavity (e.g., between two parallel mirrors) under the right conditions. For vibrational strong coupling, microfluidic IR cells can be used to study the consequences for chem. in the liq. phase. Examples of modified properties are given to demonstrate the full potential for the mol. and material sciences. Finally an outlook of future directions for this emerging subject is given.
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Orgiu, E.; George, J.; Hutchison, J. A.; Devaux, E.; Dayen, J. F.; Doudin, B.; Stellacci, F.; Genet, C.; Schachenmayer, J.; Genes, C.; Pupillo, G.; Samori, P.; Ebbesen, T. W. Conductivity in organic semiconductors hybridized with the vacuum field. Nat. Mater. 2015, 14, 1123– 1129, DOI: 10.1038/nmat4392
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Conductivity in organic semiconductors hybridized with the vacuum field
Orgiu, E.; George, J.; Hutchison, J. A.; Devaux, E.; Dayen, J. F.; Doudin, B.; Stellacci, F.; Genet, C.; Schachenmayer, J.; Genes, C.; Pupillo, G.; Samori, P.; Ebbesen, T. W.
Nature Materials (2015), 14 (11), 1123-1129CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
Much effort over the past decades was focused on improving carrier mobility in org. thin-film transistors by optimizing the organization of the material or the device architecture. Here the authors take a different path to solving this problem, by injecting carriers into states that are hybridized to the vacuum electromagnetic field. To test this idea, org. semiconductors were strongly coupled to plasmonic modes to form coherent states that can extend over as many as 105 mols. and should thereby favor cond. Indeed the current does increase by an order of magnitude at resonance in the coupled state, reflecting mostly a change in field-effect mobility. A theor. quantum model confirms the delocalization of the wavefunctions of the hybridized states and its effect on the cond. The authors' findings illustrate the potential of engineering the vacuum electromagnetic environment to modify and to improve properties of materials.
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Feist, J.; García-Vidal, F. J. Extraordinary exciton conductance induced by strong coupling. Phys. Rev. Lett. 2015, 114, 196402, DOI: 10.1103/PhysRevLett.114.196402
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Extraordinary exciton conductance induced by strong coupling
Feist, Johannes; Garcia-Vidal, Francisco J.
Physical Review Letters (2015), 114 (19), 196402/1-196402/5CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
We demonstrate that exciton conductance in org. materials can be enhanced by several orders of magnitude when the mols. are strongly coupled to an electromagnetic mode. Using a 1D model system, we show how the formation of a collective polaritonic mode allows excitons to bypass the disordered array of mols. and jump directly from one end of the structure to the other. This finding could have important implications in the fields of exciton transistors, heat transport, photosynthesis, and biol. systems in which exciton transport plays a key role.
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Schachenmayer, J.; Genes, C.; Tignone, E.; Pupillo, G. Cavity-enhanced transport of excitons. Phys. Rev. Lett. 2015, 114, 196403, DOI: 10.1103/PhysRevLett.114.196403
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Cavity-enhanced transport of excitons
Schachenmayer, Johannes; Genes, Claudiu; Tignone, Edoardo; Pupillo, Guido
Physical Review Letters (2015), 114 (19), 196403/1-196403/6CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
We show that exciton-type transport in certain materials can be dramatically modified by their inclusion in an optical cavity: the modification of the electromagnetic vacuum mode structure introduced by the cavity leads to transport via delocalized polariton modes rather than through tunneling processes in the material itself. This can help overcome exponential suppression of transmission properties as a function of the system size in the case of disorder and other imperfections. We exemplify massive improvement of transmission for excitonic wave packets through a cavity, as well as enhancement of steady-state exciton currents under incoherent pumping. These results may have implications for expts. of exciton transport in disordered org. materials. We propose that the basic phenomena can be obsd. in quantum simulators made of Rydberg atoms, cold mols. in optical lattices, as well as in expts. with trapped ions.
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Schlawin, F.; Cavalleri, A.; Jaksch, D. Cavity-mediated electron-photon superconductivity. Phys. Rev. Lett. 2019, 122, 133602, DOI: 10.1103/PhysRevLett.122.133602
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Cavity-Mediated Electron-Photon Superconductivity
Schlawin, Frank; Cavalleri, Andrea; Jaksch, Dieter
Physical Review Letters (2019), 122 (13), 133602CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)
A review. We investigate electron paring in a two-dimensional electron system mediated by vacuum fluctuations inside a nanoplasmonic terahertz cavity. We show that the structured cavity vacuum can induce long-range attractive interactions between current fluctuations which lead to pairing in generic materials with crit. temps. in the low-kelvin regime for realistic parameters. The induced state is a pair-d. wave superconductor which can show a transition from a fully gapped to a partially gapped phase-akin to the pseudogap phase in high-Tc superconductors. Our findings provide a promising tool for engineering intrinsic electron interactions in two-dimensional materials.
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22
Coles, D. M.; Somaschi, N.; Michetti, P.; Clark, C.; Lagoudakis, P. G.; Savvidis, P. G.; Lidzey, D. G. Polariton-mediated energy transfer between organic dyes in a strongly coupled optical microcavity. Nat. Mater. 2014, 13, 712– 719, DOI: 10.1038/nmat3950
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22
Polariton-mediated energy transfer between organic dyes in a strongly coupled optical microcavity
Coles, David M.; Somaschi, Niccolo; Michetti, Paolo; Clark, Caspar; Lagoudakis, Pavlos G.; Savvidis, Pavlos G.; Lidzey, David G.
Nature Materials (2014), 13 (7), 712-719CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
Strongly coupled optical microcavities contg. different exciton states permit the creation of hybrid-polariton modes that can be described in terms of a linear admixt. of cavity-photon and the constituent excitons. Such hybrid states were predicted to have optical properties that are different from their constituent parts, making them a test bed for the exploration of light-matter coupling. Here, we use strong coupling in an optical microcavity to mix the electronic transitions of 2 J-aggregated mol. dyes and use both non-resonant photoluminescence emission and photoluminescence excitation spectroscopy to show that hybrid-polariton states act as an efficient and ultrafast energy-transfer pathway between the 2 exciton states. We argue that this type of structure may act as a model system to study energy-transfer processes in biol. light-harvesting complexes.
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Zhong, X.; Chervy, T.; Wang, S.; George, J.; Thomas, A.; Hutchison, J. A.; Devaux, E.; Genet, C.; Ebbesen, T. W. Non-radiative energy transfer mediated by hybrid light-matter states. Angew. Chem., Int. Ed. 2016, 55, 6202, DOI: 10.1002/anie.201600428
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23
Non-Radiative Energy Transfer Mediated by Hybrid Light-Matter States
Zhong, Xiaolan; Chervy, Thibault; Wang, Shaojun; George, Jino; Thomas, Anoop; Hutchison, James A.; Devaux, Eloise; Genet, Cyriaque; Ebbesen, Thomas W.
Angewandte Chemie, International Edition (2016), 55 (21), 6202-6206CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
Direct evidence is presented of enhanced nonradiative energy transfer between 2 J-aggregated cyanine dyes strongly coupled to the vacuum field of a cavity. Excitation spectroscopy and fs pump-probe measurements show that the energy transfer is highly efficient when both the donor and acceptor form light-matter hybrid states with the vacuum field. The rate of energy transfer is increased by a factor of 7 under those conditions as compared to the normal situation outside the cavity, with a corresponding effect on the energy transfer efficiency. The delocalized hybrid states connect the donor and acceptor mols. and clearly play the role of a bridge to enhance the rate of energy transfer. This finding has fundamental implications for coherent energy transport and light-energy harvesting.
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Zhong, X.; Chervy, T.; Zhang, L.; Thomas, A.; George, J.; Genet, C.; Hutchison, J. A.; Ebbesen, T. W. Energy transfer between spatially separated entangled molecules. Angew. Chem., Int. Ed. 2017, 56, 9034, DOI: 10.1002/anie.201703539
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24
Energy Transfer between Spatially Separated Entangled Molecules
Zhong, Xiaolan; Chervy, Thibault; Zhang, Lei; Thomas, Anoop; George, Jino; Genet, Cyriaque; Hutchison, James A.; Ebbesen, Thomas W.
Angewandte Chemie, International Edition (2017), 56 (31), 9034-9038CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
Light-matter strong coupling allows for the possibility of entangling the wave functions of different mols. through the light field. We hereby present direct evidence of non-radiative energy transfer well beyond the Foerster limit for spatially sepd. donor and acceptor cyanine dyes strongly coupled to a cavity. The transient dynamics and the static spectra show an energy transfer efficiency approaching 37% for donor-acceptor distances ≥100 nm. In such systems, the energy transfer process becomes independent of distance as long as the coupling strength is maintained. This is consistent with the entangled and delocalized nature of the polaritonic states.
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Du, M.; Martínez-Martínez, M. A.; Ribeiro, R. F.; Hu, Z.; Menon, V. M.; Yuen-Zhou, J. Theory for polariton-assisted remote energy transfer. Chem. Sci. 2018, 9, 6659– 6669, DOI: 10.1039/C8SC00171E
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25
Theory for polariton-assisted remote energy transfer
Du, Matthew; Martinez-Martinez, Luis A.; Ribeiro, Raphael F.; Hu, Zixuan; Menon, Vinod M.; Yuen-Zhou, Joel
Chemical Science (2018), 9 (32), 6659-6669CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
Strong-coupling between light and matter produces hybridized states (polaritons) whose delocalization and electromagnetic character allow for novel modifications in spectroscopy and chem. reactivity of mol. systems. Recent expts. have demonstrated remarkable distance-independent long-range energy transfer between mols. strongly coupled to optical microcavity modes. To shed light on the mechanism of this phenomenon, we present the first comprehensive theory of polariton-assisted remote energy transfer (PARET) based on strong-coupling of donor and/or acceptor chromophores to surface plasmons. Application of our theory demonstrates that PARET up to a micron is indeed possible. In particular, we report two regimes for PARET: in one case, strong-coupling to a single type of chromophore leads to transfer mediated largely by surface plasmons while in the other case, strong-coupling to both types of chromophores creates energy transfer pathways mediated by vibrational relaxation. Importantly, we highlight conditions under which coherence enhances or deteriorates these processes. For instance, while exclusive strong-coupling to donors can enhance transfer to acceptors, the reverse turns out not to be true. However, strong-coupling to acceptors can shift energy levels in a way that transfer from acceptors to donors can occur, thus yielding a chromophore role-reversal or "carnival effect". This theor. study demonstrates the potential for confined electromagnetic fields to control and mediate PARET, thus opening doors to the design of remote mesoscale interactions between mol. systems.
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Sáez-Blázquez, R.; Feist, J.; Fernández-Domínguez, A. I.; García-Vidal, F. J. Organic polaritons enable local vibrations to drive long-range energy transfer. Phys. Rev. B: Condens. Matter Mater. Phys. 2018, 97, 241407R, DOI: 10.1103/PhysRevB.97.241407
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There is no corresponding record for this reference.
27
Gonzalez-Ballestero, C.; Feist, J.; Moreno, E.; Garcia-Vidal, F. J. Harvesting excitons through plasmonic strong coupling. Phys. Rev. B: Condens. Matter Mater. Phys. 2015, 92, 121402R, DOI: 10.1103/PhysRevB.92.121402
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27
Harvesting excitons through plasmonic strong coupling
Gonzalez-Ballestero, Carlos; Feist, Johannes; Moreno, Esteban; Garcia-Vidal, Francisco J.
Physical Review B: Condensed Matter and Materials Physics (2015), 92 (12), 121402/1-121402/5CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
Exciton harvesting is demonstrated in an ensemble of quantum emitters coupled to localized surface plasmons. When the interaction between emitters and the dipole mode of a metallic nanosphere reaches the strong-coupling regime, the exciton conductance is greatly increased. The spatial map of the conductance matches the plasmon field intensity profile, which indicates that transport properties can be tuned by adequately tailoring the field of the plasmonic resonance. Under strong coupling, we find that pure dephasing can have detrimental or beneficial effects on the conductance, depending on the effective no. of participating emitters. Finally, we show that the exciton transport in the strong-coupling regime occurs on an ultrafast time scale given by the inverse Rabi splitting (∼10 fs), which is orders of magnitude faster than transport through direct hopping between the emitters.
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García-Vidal, F. J.; Feist, J. Long-distance operator for energy transfer. Science 2017, 357, 1357– 1358, DOI: 10.1126/science.aao4268
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28
Long-distance operator for energy transfer
Garcia-Vidal, Francisco J.; Feist, Johannes
Science (Washington, DC, United States) (2017), 357 (6358), 1357-1358CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
There is no expanded citation for this reference.
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Wientjes, E.; Renger, J.; Curto, A. G.; Cogdell, R.; van Hulst, N. F. Strong antenna-enhanced fluorescence of a single light-harvesting complex shows photon antibunching. Nat. Commun. 2014, 5, 4236, DOI: 10.1038/ncomms5236
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29
Strong antenna-enhanced fluorescence of a single light-harvesting complex shows photon antibunching
Wientjes, Emilie; Renger, Jan; Curto, Alberto G.; Cogdell, Richard; van Hulst, Niek F.
Nature Communications (2014), 5 (), 4236CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)
The nature of the highly efficient energy transfer in photosynthetic light-harvesting complexes is a subject of intense research. Unfortunately, the low fluorescence efficiency and limited photostability hampers the study of individual light-harvesting complexes at ambient conditions. Here, we demonstrate an over 500-fold fluorescence enhancement of light-harvesting complex 2 (LH2) at the single-mol. level by coupling to a gold nanoantenna. The resonant antenna produces an excitation enhancement of circa 100 times and a fluorescence lifetime shortening to ∼\n20 ps. The radiative rate enhancement results in a 5.5-fold-improved fluorescence quantum efficiency. Exploiting the unique brightness, we have recorded the first photon antibunching of a single light-harvesting complex under ambient conditions, showing that the 27 bacteriochlorophylls coordinated by LH2 act as a non-classical single-photon emitter. The presented bright antenna-enhanced LH2 emission is a highly promising system to study energy transfer and the role of quantum coherence at the level of single complexes.
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Wientjes, E.; Renger, J.; Cogdell, R.; van Hulst, N. F. Pushing the photon limit: nanoantennas increase maximal photon stream and total photon number. J. Phys. Chem. Lett. 2016, 7, 1604– 1609, DOI: 10.1021/acs.jpclett.6b00491
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30
Pushing the Photon Limit: Nanoantennas Increase Maximal Photon Stream and Total Photon Number
Wientjes, Emilie; Renger, Jan; Cogdell, Richard; van Hulst, Niek F.
Journal of Physical Chemistry Letters (2016), 7 (9), 1604-1609CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
Nanoantennas are known for their effective role in fluorescence enhancement, both in excitation and emission. Enhancements of 3-4 orders of magnitude were reported. Yet in practice, the photon emission is limited by satn. due to the time that a mol. spends in singlet and esp. triplet excited states. The max. photon stream restricts the attainable enhancement. The total no. of photons emitted is limited by photobleaching. The limited brightness and observation time are a drawback for applications, esp. in biol. This photon limit is challenged, showing that nanoantennas can actually increase both satn. intensity and photostability. So far, this limit-shifting role of nanoantennas has hardly been explored. Single light-harvesting complexes, under satg. excitation conditions, show >50-fold antenna-enhanced photon emission stream, with 10-fold more total photons, ≤108 detected photons, before photobleaching. This work shows yet another facet of the great potential of nanoantennas in the world of single-mol. biol.
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31
Tsargorodska, A.; Cartron, M. L.; Vasilev, C.; Kodali, G.; Mass, O. A.; Baumberg, J. J.; Dutton, P. L.; Hunter, C. N.; Törmä, P.; Leggett, G. J. Strong coupling of localized surface plasmons to excitons in light-harvesting complexes. Nano Lett. 2016, 16, 6850– 6856, DOI: 10.1021/acs.nanolett.6b02661
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31
Strong Coupling of Localized Surface Plasmons to Excitons in Light-Harvesting Complexes
Tsargorodska, Anna; Cartron, Michael L.; Vasilev, Cvetelin; Kodali, Goutham; Mass, Olga A.; Baumberg, Jeremy J.; Dutton, P. Leslie; Hunter, C. Neil; Torma, Paivi; Leggett, Graham J.
Nano Letters (2016), 16 (11), 6850-6856CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
Gold nanostructure arrays exhibit surface plasmon resonances that split after attaching light harvesting complexes 1 and 2 (LH1 and LH2) from purple bacteria. The splitting is attributed to strong coupling between the localized surface plasmon resonances and excitons in the light-harvesting complexes. Wild-type and mutant LH1 and LH2 from Rhodobacter sphaeroides contg. different carotenoids yield different splitting energies, demonstrating that the coupling mechanism is sensitive to the electronic states in the light harvesting complexes. Plasmon-exciton coupling models reveal different coupling strengths depending on the mol. organization and the protein coverage, consistent with strong coupling. Strong coupling was also obsd. for self-assembling polypeptide maquettes that contain only chlorins. However, it is not obsd. for monolayers of bacteriochlorophyll, indicating that strong plasmon-exciton coupling is sensitive to the specific presentation of the pigment mols.
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Caprasecca, S.; Corni, S.; Mennucci, B. Shaping excitons in light-harvesting proteins through nanoplasmonics. Chem. Sci. 2018, 9, 6219– 6227, DOI: 10.1039/C8SC01162A
[Crossref], [PubMed], [CAS], Google Scholar
32
Shaping excitons in light-harvesting proteins through nanoplasmonics
Caprasecca, Stefano; Corni, Stefano; Mennucci, Benedetta
Chemical Science (2018), 9 (29), 6219-6227CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
Nanoplasmonics has been used to enhance mol. spectroscopic signals, with exquisite spatial resoln. down to the sub-mol. scale. By means of a rigorous, state-of-the-art multiscale model based on a quantum chem. description, here we show that optimally tuned tip-shaped metal nanoparticles can selectively excite localized regions of typically coherent systems, eventually narrowing down to probing one single pigment. The well-known major light-harvesting complex LH2 of purple bacteria has been investigated because of its unique properties, as it presents both high and weak delocalization among subclusters of pigments. This finding opens the way to the direct spectroscopic investigation of quantum-based processes, such as the quantum diffusion of the excitation among the chromophores, and their external manipulation.
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Coles, D. M.; Yang, Y.; Wang, Y.; Grant, R. T.; Taylor, R. A.; Saikin, S. K.; Aspuru-Guzik, A.; Lidzey, D. G.; Tang, J. K.-H.; Smith, J. M. Strong coupling between chlorosomes of photosynthetic bacteria and a confined optical cavity mode. Nat. Commun. 2014, 5, 5561, DOI: 10.1038/ncomms6561
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33
Strong coupling between chlorosomes of photosynthetic bacteria and a confined optical cavity mode
Coles, David M.; Yang, Yanshen; Wang, Yaya; Grant, Richard T.; Taylor, Robert A.; Saikin, Semion K.; Aspuru-Guzik, Alan; Lidzey, David G.; Tang, Joseph Kuo-Hsiang; Smith, Jason M.
Nature Communications (2014), 5 (), 5561CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)
Strong exciton-photon coupling is the result of a reversible exchange of energy between an excited state and a confined optical field. This results in the formation of polariton states that have energies different from the exciton and photon. We demonstrate strong exciton-photon coupling between light-harvesting complexes and a confined optical mode within a metallic optical microcavity. The energetic anti-crossing between the exciton and photon dispersions characteristic of strong coupling is obsd. in reflectivity and transmission with a Rabi splitting energy on the order of 150 meV, which corresponds to about 1000 chlorosomes coherently coupled to the cavity mode. We believe that the strong coupling regime presents an opportunity to modify the energy transfer pathways within photosynthetic organisms without modification of the mol. structure.
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Coles, D.; Flatten, L. C.; Sydney, T.; Hounslow, E.; Saikin, S. K.; Aspuru-Guzik, A.; Vedral, V.; Tang, J. K. H.; Taylor, R. A.; Smith, J. M.; Lidzey, D. G. A nanophotonic structure containing living photosynthetic bacteria. Small 2017, 13, 1701777, DOI: 10.1002/smll.201701777
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35
Bloch, F. Generalized theory of relaxation. Phys. Rev. 1957, 105, 1206, DOI: 10.1103/PhysRev.105.1206
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35
Generalized theory of relaxation
Bloch, F.
Physical Review (1957), 105 (), 1206-22CODEN: PHRVAO; ISSN:0031-899X.
cf. C.A. 47, 7307i. A further generalization is given of the earlier theory.
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36
Redfield, A. G. On the theory of relaxation processes. IBM J. Res. Dev. 1957, 1, 19, DOI: 10.1147/rd.11.0019
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There is no corresponding record for this reference.
37
Ritz, T.; Park, S.; Schulten, K. Kinetics of excitation migration and trapping in the photosynthetic unit of purple bacteria. J. Phys. Chem. B 2001, 105, 8259– 8267, DOI: 10.1021/jp011032r
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37
Kinetics of Excitation Migration and Trapping in the Photosynthetic Unit of Purple Bacteria
Ritz, Thorsten; Park, Sanghyun; Schulten, Klaus
Journal of Physical Chemistry B (2001), 105 (34), 8259-8267CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)
Purple bacteria have developed an efficient app. to harvest sunlight. The app. consists of up to four types of pigment-protein complexes: (i) the photosynthetic reaction center surrounded by (ii) the light-harvesting complex LH1, (iii) antenna complexes LH2, which are replaced under low-light conditions by (iv) antenna complexes LH3 with a higher absorption max. Following absorption of light anywhere in the app., electronic excitation is transferred between the pigment-protein complexes until it is used for the primary photoreaction in the reaction center. We calc., using F.ovrddot.orster theory, all rates for the inter-complex excitation transfer processes on the basis of the at. level structures of the pigment-protein complexes and of an effective Hamiltonian, established previously, for intracomplex excitations. The kinetics of excitation migration in the photosynthetic app. is described through a master equation which connects the calcd. transfer rates to the overall architecture of the app. For two exemplary architectures the efficiency, distribution of dissipation, and time evolution of excitation migration are detd. Pigment-protein complexes are found to form an excitation reservoir, in which excitation is spread over many chromophores rather than forming an excitation funnel in which excitation is transferred without detours from the periphery to the RC. This feature permits a high quantum yield of 83% to 89%, but also protects the app. from overheating by spreading dissipation over all complexes. Substitution of LH2 complexes by LH3 complexes or changing an architecture in which few LH2 (LH3) complexes are in contact with LH1 to an architecture in which all LH2 (LH3) complexes are in contact with LH1 increases the quantum yield up to 94% and decreases the degree to which dissipation is evenly distributed.
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Caycedo-Soler, F.; Schroeder, C. A.; Autenrieth, C.; Pick, A.; Ghosh, R.; Huelga, S. F.; Plenio, M. B. Quantum redirection of antenna absorption to photosynthetic reaction centers. J. Phys. Chem. Lett. 2017, 8, 6015– 6021, DOI: 10.1021/acs.jpclett.7b02714
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38
Quantum redirection of antenna absorption to photosynthetic reaction centers
Caycedo-Soler, Felipe; Schroeder, Christopher A.; Autenrieth, Caroline; Pick, Arne; Ghosh, Robin; Huelga, Susana F.; Plenio, Martin B.
Journal of Physical Chemistry Letters (2017), 8 (24), 6015-6021CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
The early steps of photosynthesis involve the photoexcitation of reaction centers (RCs) and light-harvesting (LH) units. Here, we show that the historically overlooked excitonic delocalization across RC and LH pigments results in a redistribution of absorption amplitudes that benefits the absorption cross-section of the optical bands assocd. with the RC of several species. While we proved that this redistribution is robust to the microscopic details of the dephasing between these units in the purple bacterium, Rhodospirillum rubrum, we were able to show that the redistribution witnessed a more fragile, but persistent, coherent population dynamics which directed excitations from the LH toward the RC units under incoherent illumination and physiol. conditions. Even though the redirection did not seem to affect importantly the overall efficiency in photosynthesis, stochastic optimization allowed us to delineate clear guidelines and develop simple analytic expressions in order to amplify the coherent redirection in artificial nanostructures.
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McDermott, G.; Prince, S. M.; Freer, A. A.; Hawthornthwaite-Lawless, A. M.; Papiz, M. Z.; Cogdell, R. J.; Isaacs, N. W. Crystal structure of an integral membrane light-harvesting complex from photosynthetic bacteria. Nature 1995, 374, 517– 521, DOI: 10.1038/374517a0
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39
Crystal structure of an integral membrane light-harvesting complex from photosynthetic bacteria
McDermott, G.; Prince, S. M.; Freer, A. A.; Hawthornthwaite-Lawless, A. M.; Papiz, M. Z.; Cogdell, R. J.; Isaacs, N. W.
Nature (London) (1995), 374 (6522), 517-21CODEN: NATUAS; ISSN:0028-0836. (Macmillan Magazines)
The crystal structure of the light-harvesting antenna complex (LH2) from Rhodopseudomonas acidophila strain 10050 shows that the active assembly consists of two concentric cylinders of helical protein subunits which enclose the pigment mols. Eighteen bacteriochlorophyll a mols. sandwiched between the helixes form a continuous overlapping ring, and a further nine are positioned between the outer helixes with the bacteriochlorin rings perpendicular to the transmembrane helix axis. There is an elegant intertwining of the bacteriochlorophyll phytol chains with carotenoid, which spans the complex.
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Cupellini, L.; Jurinovich, S.; Campetella, M.; Caprasecca, S.; Guido, C. A.; Kelly, S. M.; Gardiner, A. T.; Cogdell, R.; Mennucci, B. An ab initio description of the excitonic properties of LH2 and their temperature dependence. J. Phys. Chem. B 2016, 120, 11348– 11359, DOI: 10.1021/acs.jpcb.6b06585
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40
An ab initio description of the excitonic properties of LH2 and their temperature dependence
Cupellini, Lorenzo; Jurinovich, Sandro; Campetella, Marco; Caprasecca, Stefano; Guido, Ciro A.; Kelly, Sharon M.; Gardiner, Alastair T.; Cogdell, Richard; Mennucci, Benedetta
Journal of Physical Chemistry B (2016), 120 (44), 11348-11359CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
The spectroscopic properties of light-harvesting (LH) antennae in photosynthetic organisms represent a fingerprint that is unique for each specific pigment-protein complex. Because of that, spectroscopic observations are generally combined with structural data from x-ray crystallog. to obtain an indirect representation of the excitonic properties of the system. Here, an alternative strategy is presented which goes beyond this empirical approach and introduces an ab initio computational description of both structural and electronic properties and their dependence on the temp. The strategy was applied to the peripheral light-harvesting antenna complex (LH2) present in purple bacteria. By comparing this model with the one based on the crystal structure, a detailed, mol. level explanation of the absorption and CD spectra and their temp. dependence was achieved. The agreement obtained with the expts. at both low and room temp. lays the groundwork for an atomistic understanding of the excitation dynamics in the LH2 system.
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Caycedo-Soler, F.; Lim, F.; Oviedo-Casado, S.; van Hulst, N. F.; Huelga, S. F.; Plenio, M. B. Theory of excitonic delocalization for robust vibronic dynamics in LH2. J. Phys. Chem. Lett. 2018, 9, 3446– 3453, DOI: 10.1021/acs.jpclett.8b00933
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Theory of Excitonic Delocalization for Robust Vibronic Dynamics in LH2
Caycedo-Soler, Felipe; Lim, James; Oviedo-Casado, Santiago; van Hulst, Niek F.; Huelga, Susana F.; Plenio, Martin B.
Journal of Physical Chemistry Letters (2018), 9 (12), 3446-3453CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
Nonlinear spectroscopy has revealed long-lasting oscillations in the optical response of a variety of photosynthetic complexes. Different theor. models that involve the coherent coupling of electronic (excitonic) or electronic-vibrational (vibronic) degrees of freedom have been put forward to explain these observations. The ensuing debate concerning the relevance of either mechanism may have obscured their complementarity. To illustrate this balance, we quantify how the excitonic delocalization in the LH2 unit of Rhodopseudomonas acidophila purple bacterium leads to correlations of excitonic energy fluctuations, relevant coherent vibronic coupling, and importantly, a decrease in the excitonic dephasing rates. Combining these effects, we identify a feasible origin for the long-lasting oscillations obsd. in fluorescent traces from time-delayed two-pulse single-mol. expts. performed on this photosynthetic complex and use this approach to discuss the role of this complementarity in other photosynthetic systems.
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Zazubovich, V.; Tibe, I.; Small, G. J. Bacteriochlorophyll a Franck-Condon Factors for the S0→S1(Qy) Transition. J. Phys. Chem. B 2001, 105, 12410– 12417, DOI: 10.1021/jp012804m
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42
Bacteriochlorophyll a Franck-Condon Factors for the S0 → S1(Qy) Transition
Zazubovich, V.; Tibe, I.; Small, G. J.
Journal of Physical Chemistry B (2001), 105 (49), 12410-12417CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)
Pseudovibronic satellite hole-burning spectroscopy of bacteriochlorophyll a (BChl a) in two glasses at 5 K was used to det. the Franck-Condon (FC) factors for 56 one-quantum (0 → 1) vibrational transitions that lie between 160 and 1600 cm-1. As in the case of Chl a (Pieper, J.; et al. J. Phys. Chem. B 1999, 103, 2319), the FC factors are small, ranging between 0.05 and 0.0007 (uncertainty ≈ ±20%). The FC factors, together with the exptl. detd. inhomogeneous site excitation distribution function for the zero-phonon line and linear electron-phonon coupling parameters, account well for the S0 → Qy absorption spectra. Thus, the FC factors are accurate enough to be used in quantum mech. calcns. of excitation energy transfer rates in photosynthetic antenna complexes (with their intrinsic structural heterogeneity) exhibiting excitonic coupling that ranges between weak and strong. The BChl a FC factors detd. by hole burning are compared with those obtained by fluorescence line narrowing spectroscopy (Wendling, M.; et al. J. Phys. Chem. B 2000, 104, 5825). The latter, which are about a factor of 5 smaller than those detd. by hole burning, are too small to account for the vibronic contribution to the S0 → Qy absorption spectrum. The discrepancy between the two sets of FC factors is discussed.
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De Caro, C.; Visschers, R. W.; van Grondelle, R.; Völker, S. Inter- and intraband energy transfer in LH2-antenna complexes of purple bacteria. A fluorescence line-narrowing and hole-burning study. J. Phys. Chem. 1994, 98, 10584– 10590, DOI: 10.1021/j100092a032
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43
Inter- and Intraband Energy Transfer in LH2-Antenna Complexes of Purple Bacteria. A Fluorescence Line-Narrowing and Hole-Burning Study
De Caro, C.; Visschers, R. W.; van Grondelle, R.; Voelker, S.
Journal of Physical Chemistry (1994), 98 (41), 10584-90CODEN: JPCHAX; ISSN:0022-3654.
High-resoln. site-selection fluorescence- and hole-burning spectroscopy were used to study energy transfer in two LH2 light-harvesting complexes of purple bacteria: the B800-850 complex of isolated Rhodobacter sphaeroides and the B800-820 complex of Rhodopseudomonas acidophila, at 1.2 K. Fluorescence spectra, hole widths, and hole depths were measured as a function of excitation wavelength λexc within the B800 band. For λexc ≥ 798 nm, fluorescence line-narrowing is obsd. and the energy-transfer times (τ = 2.5 and 2.0 ps for B800-850 and B800-820, resp.) are independent of λexc. In this spectral region only interband B800 → B850 (B820) energy transfer takes place. For 780 nm ≤ λexc ≤ 798 nm, the fluorescence bands are broad and the transfer time, obtained from hole widths extrapolated to zero burning-fluence d., decreases toward the blue side of B800. In this wavelength region competition occurs between B800 → B850 (B820) and B800 → B800 "downhill" energy transfer. For λexc ≤ 780 nm, the broad fluorescence bands, with maxima at λem ∼805 nm, become independent of λexc and intraband B800 → B800 transfer combined with excited-state vibrational relaxation are the dominant processes. The spectral distribution of the most-red absorbing pigments within the B800 band, which transfer energy exclusively from B800to B850 (B820), was detd. from the depth of the hole vs. λexc. The results indicate that one-third of the B800 pigments transfer their energy only to B850 (B820), from which it is concluded that the minimal functional LH2-unit consists of at least three B800 pigments and six B850 pigments, in addn. to carotenoids.
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44
Sauer, K.; Cogdell, R. J.; Prince, S. M.; Freer, A.; Isaacs, N. W.; Scheer, H. Structure-based calculations of the optical spectra of the LH2 bacteriochlorophyll-protein complex from Rhodopseudomonas acidophila. Photochem. Photobiol. 1996, 64, 564– 576, DOI: 10.1111/j.1751-1097.1996.tb03106.x
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Structure-based calculations of the optical spectra of the LH2 bacteriochlorophyll-protein complex from Rhodopseudomonas acidophila
Sauer, Kenneth; Cogdell, Richard J.; Prince, Steve M.; Freer, Andy; Isaacs, Neil W.; Scheer, Hugo
Photochemistry and Photobiology (1996), 64 (3), 564-576CODEN: PHCBAP; ISSN:0031-8655. (American Society for Photobiology)
The mol. structure of the light-harvesting complex 2 (LH2) bacteriochlorophyll-protein antenna complex from the purple non-sulfur photosynthetic bacterium R. acidophila, strain 10050 provides the positions and orientations of the 27 bacteriochlorophyll (BChl) mols. in the complex. Our structure-based model calcns. of the distinctive optical properties (absorption, CD, polarization) of LH2 in the near-IR region use a point-monopole approxn. to represent the BChl Qy transition moment. The results of the calcns. support the assignment of the ring of 18 closely coupled BChl to B850 (BChl absorbing at 850 nm) and the larger diam., parallel ring of 9 weakly coupled BChl to B800. All of the significantly allowed transitions in the near-IR-are calcd. to be perpendicular to the C9 symmetry axis, in agreement with polarization studies of this membrane-assocd. complex. To match the absorption maxima of the B800 and B850 components using a relative permittivity (dielec. const.) of 2.1, we assign different site energies (12,500 and 12,260 cm-1, resp.) for the Qy transitions of the resp. BChl in their protein binding sites. Excitonic coupling is particularly strong among the set of B850 chromophores, with pairwise interaction energies nearly 300 cm-1 between nearest neighbors, comparable with the exptl. absorption bandwidths at room temp. These strong interactions, for the full set of 18 B850 chromophores, result in an excitonic manifold that is 1200 cm-1 wide. Some of the upper excitonic states should result in weak absorption and perhaps stronger CD features. These predictions from the calcns. await exptl. verification.
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Tretiak, S.; Middleton, C.; Chernyak, V.; Mukamel, S. Bacteriochlorophyll and carotenoid excitonic couplings in the LH2 system of purple bacteria. J. Phys. Chem. B 2000, 104, 9540– 9553, DOI: 10.1021/jp001585m
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Bacteriochlorophyll and carotenoid excitonic couplings in the LH2 system of purple bacteria
Tretiak, Sergei; Middleton, Chris; Chernyak, Vladimir; Mukamel, Shaul
Journal of Physical Chemistry B (2000), 104 (40), 9540-9553CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)
An effective Frenkel-exciton Hamiltonian for the entire LH2 photosynthetic complex (B800, B850, and carotenoids) from Rhodospirillum molischianum is calcd. by combining the crystal structure with the Collective Electronic Oscillators (CEO) algorithm for optical response. Electronic couplings among all pigments are computed for the isolated complex and in a dielec. medium, whereby the protein environment contributions are incorporated using the Self-Consistent Reaction Field approach. The absorption spectra are analyzed by computing the electronic structure of the bacteriochlorophylls and carotenoids forming the complex. Interchromophore electronic couplings are then calcd. using both a spectroscopic approach, which derives couplings from Davydov's splittings in the dimer spectra, and an electrostatic approach, which directly computes the Coulomb integrals between transition densities of each chromophore. A comparison of the couplings obtained using these two methods allows for the sepn. of the electrostatic (F.ovrddot.orster) and electron exchange (Dexter) contributions. The significant impact of solvation on intermol. interactions reflects the need for properly incorporating the protein environment in accurate computations of electronic couplings. The F.ovrddot.orster incoherent energy transfer rates among the weakly coupled B800-B800, B800-B850, Lyc-B850, and Lyc-B850 mols. are calcd., and the effects of the dielec. medium on the LH2 light-harvesting function are analyzed and discussed.
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46
Linnanto, J.; Korppi-Tommola, J. E. I.; Helenius, V. M. Electronic States, Absorption spectrum and circular dichroism spectrum of the photosynthetic bacterial LH2 antenna of Rhodopseudomonas acidophilas predicted by exciton theory and semiempirical calculations. J. Phys. Chem. B 1999, 103, 8739– 8750, DOI: 10.1021/jp9848344
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46
Electronic states, absorption spectrum and circular dichroism spectrum of the photosynthetic bacterial LH2 antenna of Rhodopseudomonas acidophila as predicted by exciton theory and semiempirical calculations
Linnanto, J.; Korppi-Tommola, J. E. I.; Helenius, V. M.
Journal of Physical Chemistry B (1999), 103 (41), 8739-8750CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)
A new approach that uses a combination of semiempirical CI method and exciton theory to calc. electronic energies, eigenstates, absorption spectrum and CD (CD) spectrum of the LH2 antenna of Rhodopseudomonas acidophila is introduced. A statistical simulation that uses exptl. homogeneous line widths was used to account for the inhomogeneous line width of the obsd. spectrum. Including the effect of orbital overlap of the close-lying pigments of the B850 ring and the effect of the pigment protein interaction in the B800 ring allowed a successful simulation of the exptl. absorption and CD spectra of the antenna at room temp. Two exptl. parameters, the transition energy and the magnitude of the transition dipole moment of monomeric bacteriochlorophyll a (Bchl a), were used in the calcn. The dielec. const. of the protein matrix was taken as 2.1 [ε0]. The questions of localization lengths of the excitonic states and the energy transfer mechanism between the B800 and the B850 rings are discussed in light of the results obtained.
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Van Oijen, Antoine M.; Ketelaars, Martijn; Kohler, Jirgen; Aartsma, Thijs J.; Schmidt, Jan
Science (Washington, D. C.) (1999), 285 (5426), 400-402CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
Low-temp. single-mol. spectroscopic techniques were applied to a light-harvesting pigment-protein complex (LH2) from purple photosynthetic bacteria. The properties of the electronically excited states of the two circular assemblies (B800 and B850) of bacteriochlorophyll a (BChl a) pigment mols. in the individual complexes were revealed, without ensemble averaging. The results show that the excited states of the B800 ring of pigments are mainly localized on individual BChl a mols. In contrast, the absorption of a photon by the 8850 ring can be consistently described in terms of an excitation that is completely delocalized over the ring. This property may contribute to the high efficiency of energy transfer in these photosynthetic complexes.
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Science (Washington, DC, United States) (2013), 340 (6139), 1448-1451CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
The initial steps of photosynthesis comprise the absorption of sunlight by pigment-protein antenna complexes followed by rapid and highly efficient funneling of excitation energy to a reaction center. In these transport processes, signatures of unexpectedly long-lived coherences have emerged in two-dimensional ensemble spectra of various light-harvesting complexes. Here, the authors demonstrate ultrafast quantum coherent energy transfer within individual antenna complexes of a purple bacterium under physiol. conditions. They find that quantum coherences between electronically coupled energy eigenstates persist at least 400 fs and that distinct energy-transfer pathways that change with time can be identified in each complex. The data suggest that long-lived quantum coherence renders energy transfer in photosynthetic systems robust in the presence of disorder, which is a prerequisite for efficient light harvesting.
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Abstract
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Figure 1
Figure 1. (a) Sketch of the PSU considered in this work: 6 LH2 antennas, comprising 9 B800 and 18 B850 molecules each, surrounding a single LH1 complex. The insets show the two-level system exciton model of B-molecules and LH1, which experience both radiative and vibrational decay. (b) Absorption spectrum of a single LH2 complex, including disorder and inhomogeneous broadening. (c) Vibrational spectral density, S(ω), for all LH2 pigments. (d) Exciton population dynamics for the PSU in panel a in an initial state given by the superposition of excited B800 molecules in the six LH2 antennas.
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Figure 2
Figure 2. (a) Energies of the lower (LP, yellow), middle (MP₁, green, and MP₂, blue), and upper (UP, violet) polaritons versus the cavity frequency, ω_C, and for g₀ = 9 meV. (b) Coefficients representing the cavity (yellow), LH1 (red), B800 (blue), and B850 (green) content of the four polaritons in panel a as a function of ω_C.
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Figure 3
Figure 3. Exciton dynamics for the PSU in Figure 1. (a) LH1 population versus time after the initial excitation of the B800 molecules for the PSU isolated (dashed line) and coupled to an optical cavity with ω_C = 1.6 eV and g₀ = 9 meV (solid line). The thin solid line plots the LH1 population for an initial excitation of the cavity mode. (b) Temporal evolution of the ground state (black), B800 (blue), and B850 (green) populations with (solid line) and without (dashed line) cavity. The cavity population is shown in the yellow solid line. The differences between populations have been shaded in all cases to highlight the effect of strong coupling.
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Figure 4
Figure 4. (a) LH1 population averaged over the first 300 fs after the excitation of the LH2 B800 pigments versus cavity frequency and photon–exciton coupling strength. Color solid lines render contours of the magnitude ∑_αχ_α (see panel below). (b) Polariton component of B800 and LH1 excitations, χ_α = |⟨α|LH1⟩|² |⟨α|B800⟩|², with α = LP, MP₁, MP₂, and UP. (c) LH1 population 40 ps after the initial excitation of the system as a function of ω_C and g₀.
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  Chemical Reviews (Washington, DC, United States) (2017), 117 (2), 249-293CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
  A review. The process of photosynthesis is initiated by the capture of sunlight by a network of light-absorbing mols. (chromophores), which are also responsible for the subsequent funneling of the excitation energy to the reaction centers. Through evolution, genetic drift, and speciation, photosynthetic organisms have discovered many solns. for light harvesting. In this review, we describe the underlying photophys. principles by which this energy is absorbed, as well as the mechanisms of electronic excitation energy transfer (EET). First, optical properties of the individual pigment chromophores present in light-harvesting antenna complexes are introduced, and then we examine the collective behavior of pigment-pigment and pigment-protein interactions. The description of energy transfer, in particular multichromophoric antenna structures, is shown to vary depending on the spatial and energetic landscape, which dictates the relative coupling strength between constituent pigment mols. In the latter half of the article, we focus on the light-harvesting complexes of purple bacteria as a model to illustrate the present understanding of the synergetic effects leading to EET optimization of light-harvesting antenna systems while exploring the structure and function of the integral chromophores. We end this review with a brief overview of the energy-transfer dynamics and pathways in the light-harvesting antennas of various photosynthetic organisms.
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5. 5
  Romero, E.; Novoderezhkin, V. I.; van Grondelle, R. Quantum design of photosynthesis for bio-inspired solar-energy conversion. Nature 2017, 543, 355– 365, DOI: 10.1038/nature22012
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  Quantum design of photosynthesis for bio-inspired solar-energy conversion
  Romero, Elisabet; Novoderezhkin, Vladimir I.; van Grondelle, Rienk
  Nature (London, United Kingdom) (2017), 543 (7645), 355-365CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
  Photosynthesis is the natural process that converts solar photons into energy-rich products that are needed to drive the biochem. of life. Two ultrafast processes form the basis of photosynthesis: excitation energy transfer and charge sepn. Under optimal conditions, every photon that is absorbed is used by the photosynthetic organism. Fundamental quantum mechanics phenomena, including delocalization, underlie the speed, efficiency and directionality of the charge-sepn. process. At least four design principles are active in natural photosynthesis, and these can be applied practically to stimulate the development of bio-inspired, human-made energy conversion systems.
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6. 6
  Novoderezhkin, V. I.; van Grondelle, R. Physical origins and models of energy transfer in photosynthetic light-harvesting. Phys. Chem. Chem. Phys. 2010, 12, 7352– 7365, DOI: 10.1039/c003025b
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  Physical origins and models of energy transfer in photosynthetic light-harvesting
  Novoderezhkin, Vladimir I.; van Grondelle, Rienk
  Physical Chemistry Chemical Physics (2010), 12 (27), 7352-7365CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
  A quant. comparison of different energy transfer theories, i.e. modified Redfield, std. and generalized Foerster theories, as well as combined Redfield-Foerster approach, is performed. Phys. limitations of these approaches are illustrated and crit. values of the key parameters indicating their validity are found. The spectra and dynamics in two photosynthetic antenna complexes, in phycoerythrin 545 from cryptophyte algae and in trimeric LHCII complex from higher plants, were modeled at a quant. level. These two examples show how the structural organization dets. a directed energy transfer and how equilibration within antenna subunits and migration between subunits are superimposed.
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7. 7
  Ye, J.; Sun, K.; Zhao, Y.; Yu, Y.; Lee, C. K.; Cao, J. Excitonic energy transfer in light-harvesting complexes in purple bacteria. J. Chem. Phys. 2012, 136, 245104, DOI: 10.1063/1.4729786
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  Excitonic energy transfer in light-harvesting complexes in purple bacteria
  Ye, Jun; Sun, Kewei; Zhao, Yang; Yu, Yunjin; Kong Lee, Chee; Cao, Jianshu
  Journal of Chemical Physics (2012), 136 (24), 245104/1-245104/17CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
  Two distinct approaches, the Frenkel-Dirac time-dependent variation and the Haken-Strobl model, are adopted to study energy transfer dynamics in single-ring and double-ring light-harvesting (LH) systems in purple bacteria. It is found that the inclusion of long-range dipolar interactions in the two methods results in significant increase in intra- or inter-ring exciton transfer efficiency. The dependence of exciton transfer efficiency on trapping positions on single rings of LH2 (B850) and LH1 is similar to that in toy models with nearest-neighbor coupling only. However, owing to the symmetry breaking caused by the dimerization of BChls and dipolar couplings, such dependence has been largely suppressed. In the studies of coupled-ring systems, both methods reveal an interesting role of dipolar interactions in increasing energy transfer efficiency by introducing multiple intra/inter-ring transfer paths. Importantly, the time scale (4 ps) of inter-ring exciton transfer obtained from polaron dynamics is in good agreement with previous studies. In a double-ring LH2 system, non-nearest neighbor interactions can induce symmetry breaking, which leads to global and local min. of the av. trapping time in the presence of a non-zero dephasing rate, suggesting that environment dephasing helps preserve quantum coherent energy transfer when the perfect circular symmetry in the hypothetic system is broken. This study reveals that dipolar coupling between chromophores may play an important role in the high energy transfer efficiency in the LH systems of purple bacteria and many other natural photosynthetic systems. (c) 2012 American Institute of Physics.
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8. 8
  Cheng, Y.-C.; Fleming, G. R. Dynamics of light harvesting in photosynthesis. Annu. Rev. Phys. Chem. 2009, 60, 241– 62, DOI: 10.1146/annurev.physchem.040808.090259
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  Dynamics of light harvesting in photosynthesis
  Cheng, Yuan-Chung; Fleming, Graham R.
  Annual Review of Physical Chemistry (2009), 60 (), 241-262CODEN: ARPLAP; ISSN:0066-426X. (Annual Reviews Inc.)
  A review of recent theor. and exptl. advances in the elucidation of the dynamics of light harvesting in photosynthesis, focusing on recent theor. developments in structure-based modeling of electronic excitations in photosynthetic complexes and critically examg. theor. models for excitation energy transfer. Two-dimensional electronic spectroscopy and its application to the study of photosynthetic complexes, in particular the Fenna-Matthews-Olson complex from green sulfur bacteria are briefly described. This review emphasizes recent exptl. observations of long-lasting quantum coherence in photosynthetic systems and the implications of quantum coherence in natural photosynthesis.
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9. 9
  Fassioli, F.; Dinshaw, R.; Arpin, P. C.; Scholes, G. D. Photosynthetic light harvesting: excitons and coherence. J. R. Soc., Interface 2014, 11, 20130901, DOI: 10.1098/rsif.2013.0901
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  Photosynthetic light harvesting: excitons and coherence
  Fassioli, Francesca; Dinshaw, Rayomond; Arpin, Paul C.; Scholes, Gregory D.
  Journal of the Royal Society, Interface (2014), 11 (92), 20130901/1-20130901/22CODEN: JRSICU; ISSN:1742-5689. (Royal Society)
  A review. Photosynthesis begins with light harvesting, where specialized pigment-protein complexes transform sunlight into electronic excitations delivered to reaction centers to initiate charge sepn. There is evidence that quantum coherence between electronic excited states plays a role in energy transfer. In this review, we discuss how quantum coherence manifests in photosynthetic light harvesting and its implications. We begin by examg. the concept of an exciton, an excited electronic state delocalized over several spatially sepd. mols., which is the most widely available signature of quantum coherence in light harvesting. We then discuss recent results concerning the possibility that quantum coherence between electronically excited states of donors and acceptors may give rise to a quantum coherent evolution of excitations, modifying the traditional incoherent picture of energy transfer. Key to this (partially) coherent energy transfer appears to be the structure of the environment, in particular the participation of non-equil. vibrational modes. We discuss the open questions and controversies regarding quantum coherent energy transfer and how these can be addressed using new exptl. techniques.
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10. 10
  Caycedo-Soler, F.; Rodríguez, F. J.; Quiroga, L.; Johnson, N. F. Light-harvesting mechanism of bacteria exploits a critical interplay between the dynamics of transport and trapping. Phys. Rev. Lett. 2010, 104, 158302, DOI: 10.1103/PhysRevLett.104.158302
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  Light-Harvesting Mechanism of Bacteria Exploits a Critical Interplay between the Dynamics of Transport and Trapping
  Caycedo-Soler, Felipe; Rodriguez, Ferney J.; Quiroga, Luis; Johnson, Neil F.
  Physical Review Letters (2010), 104 (15), 158302/1-158302/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
  Light-harvesting bacteria Rhodospirillum photometricum were recently found to adopt strikingly different architectures depending on illumination conditions. We present analytic and numerical calcns. which explain this observation by quantifying a dynamical interplay between excitation transfer kinetics and reaction center cycling. High light-intensity membranes exploit dissipation as a photoprotective mechanism, thereby safeguarding a steady supply of chem. energy, while low light-intensity membranes efficiently process unused illumination intensity by channeling it to open reaction centers. More generally, our anal. elucidates and quantifies the trade-offs in natural network design for solar energy conversion.
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11. 11
  Timpmann, K.; Chenchiliyan, M.; Jalviste, E.; Timney, J. A.; Hunter, C. N.; Freiberg, A. Efficiency of light harvesting in a photosynthetic bacterium adapted to different levels of light. Biochim. Biophys. Acta, Bioenerg. 2014, 1837, 1835– 1846, DOI: 10.1016/j.bbabio.2014.06.007
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  Efficiency of light harvesting in a photosynthetic bacterium adapted to different levels of light
  Timpmann, Kou; Chenchiliyan, Manoop; Jalviste, Erko; Timney, John A.; Hunter, C. Neil; Freiberg, Arvi
  Biochimica et Biophysica Acta, Bioenergetics (2014), 1837 (10), 1835-1846CODEN: BBBEB4; ISSN:0005-2728. (Elsevier B. V.)
  In this study, we use the photosynthetic purple bacterium Rhodobacter sphaeroides to find out how the acclimation of photosynthetic app. to growth conditions influences the rates of energy migration toward the reaction center traps and the efficiency of charge sepn. at the reaction centers. To answer these questions we measured the spectral and picosecond kinetic fluorescence responses as a function of excitation intensity in membranes prepd. from cells grown under different illumination conditions. A kinetic model anal. yielded the microscopic rate consts. that characterize the energy transfer and trapping inside the photosynthetic unit as well as the dependence of exciton trapping efficiency on the ratio of the peripheral LH2 and core LH1 antenna complexes, and on the wavelength of the excitation light. A high quantum efficiency of trapping over 80% was obsd. in most cases, which decreased toward shorter excitation wavelengths within the near IR absorption band. At a fixed excitation wavelength the efficiency declines with the LH2/LH1 ratio. From the perspective of the ecol. habitat of the bacteria the higher population of peripheral antenna facilitates growth under dim light even though the energy trapping is slower in low light adapted membranes. The similar values for the trapping efficiencies in all samples imply a robust photosynthetic app. that functions effectively at a variety of light intensities.
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12. 12
  Hunter, C. N.; Daldal, F.; Thurnauer, M. C.; Beatty, J. T. The purple phototrophic bacteria; Springer: Netherlands, 2009.
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13. 13
  Cogdell, R. J.; Gall, A.; Köhler, J. The architecture and function of the light-harvesting apparatus of purple bacteria: from single molecules to in vivomembrane. Q. Rev. Biophys. 2006, 39, 227– 324, DOI: 10.1017/S0033583506004434
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  The architecture and function of the light-harvesting apparatus of purple bacteria: from single molecules to in vivo membranes
  Cogdell, Richard J.; Gall, Andrew; Koehler, Juergen
  Quarterly Reviews of Biophysics (2006), 39 (3), 227-324CODEN: QURBAW; ISSN:0033-5835. (Cambridge University Press)
  A review. This review describes the structures of the two major integral membrane pigment complexes, the RC-LH1 'core' and LH2 complexes, which together make up the light-harvesting system present in typical purple photosynthetic bacteria. The antenna complexes serve to absorb incident solar radiation and to transfer it to the reaction centers, where it is used to 'power' the photosynthetic redox reaction and ultimately leads to the synthesis of ATP. Our current understanding of the biosynthesis and assembly of the LH and RC complexes is described, with special emphasis on the roles of the newly described bacteriophytochromes. Using both the structural information and that obtained from a wide variety of biophys. techniques, the details of each of the different energy-transfer reactions that occur, between the absorption of a photon and the charge sepn. in the RC, are described. Special emphasis is given to show how the use of single-mol. spectroscopy has provided a more detailed understanding of the mol. mechanisms involved in the energy-transfer processes. We have tried, with the help of an Appendix, to make the details of the quantum mechanics that are required to appreciate these mol. mechanisms, accessible to math. illiterate biologists. The elegance of the purple bacterial light-harvesting system lies in the way in which it has cleverly exploited quantum mechanics.
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14. 14
  Nagarajan, V.; Parson, W. W. Excitation energy transfer between the B850 and B875 antenna complexes of Rhodobacter Sphaeroides. Biochemistry 1997, 36, 2300– 2306, DOI: 10.1021/bi962534b
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  14
  Excitation energy transfer between the B850 and B875 antenna complexes of Rhodobacter sphaeroides
  Nagarajan, V.; Parson, W. W.
  Biochemistry (1997), 36 (8), 2300-2306CODEN: BICHAW; ISSN:0006-2960. (American Chemical Society)
  Energy transfer between the B850 (LH2) and B875 (LH1) antenna complexes of a mutant strain of Rhodobacter sphaeroides lacking reaction centers is investigated by femtosecond pump-probe spectroscopy at room temp. Measurements are made at wavelengths between 810 and 910 nm at times extending to 200 ps after selective excitation of either B850 or B875. Assignments of the spectroscopic signals to the two types of antenna complex are made on the basis of measurements in strains that lack either LH1 or LH2 in addn. to reaction centers. Energy transfer from excited B850 to B875 proceeds with two time consts., 4.6 ± 0.3 and 26.3 ± 1.0 ps, but a significant fraction of the excitations remain in B850 for considerably longer times. The fast step is interpreted as hopping of energy to LH1 from an assocd. LH2 complex; the slower steps are investigated as migration of excitations in the LH2 pool preceding transfer to LH1. Transfer of excitations from B875 to B850 could not be detected, possibly suggesting that the av. no. of LH2 complexes in contact with each LH1 is small.
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15. 15
  Cleary, L.; Chen, H.; Chuang, C.; Silbey, R. J.; Cao, J. Optimal fold symmetry of LH2 rings on a photosynthetic membrane. Proc. Natl. Acad. Sci. U. S. A. 2013, 110, 8537– 8542, DOI: 10.1073/pnas.1218270110
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  Optimal fold symmetry of LH2 rings on a photosynthetic membrane
  Cleary, Liam; Chen, Hang; Chuang, Chern; Silbey, Robert J.; Cao, Jianshu
  Proceedings of the National Academy of Sciences of the United States of America (2013), 110 (21), 8537-8542, S8537/1-S8537/5CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
  An intriguing observation of photosynthetic light-harvesting systems is the N-fold symmetry of light-harvesting complex 2 (LH2) of purple bacteria. We calc. the optimal rotational configuration of N-fold rings on a hexagonal lattice and establish two related mechanisms for the promotion of max. excitation energy transfer (EET). (i) For certain fold nos., there exist optimal basis cells with rotational symmetry, extendable to the entire lattice for the global optimization of the EET network. (ii) The type of basis cell can reduce or remove the frustration of EET rates across the photosynthetic network. We find that the existence of a basis cell and its type are directly related to the no. of matching points S between the fold symmetry and the hexagonal lattice. The two complementary mechanisms provide selection criteria for the fold no. and identify groups of consecutive nos. Remarkably, one such group consists of the naturally occurring 8-, 9-, and 10-fold rings. By considering the inter-ring distance and EET rate, we demonstrate that this group can achieve minimal rotational sensitivity in addn. to an optimal packing d., achieving robust and efficient EET. This corroborates our findings i and ii and, through their direct relation to 5, suggests the design principle of matching the internal symmetry with the lattice order.
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16. 16
  Lidzey, D. G.; Bradley, D. D. C.; Skolnick, M. S.; Virgili, T.; Walker, S.; Whittaker, D. M. Strong exciton–photon coupling in an organic semiconductor microcavity. Nature 1998, 395, 53– 55, DOI: 10.1038/25692
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  Strong exciton-photon coupling in an organic semiconductor microcavity
  Lidzey, D. G.; Gradley, D. D. C.; Skolnick, M. S.; Virgili, T.; Walker, S.; Whittaker, D. M.
  Nature (London) (1998), 395 (6697), 53-55CODEN: NATUAS; ISSN:0028-0836. (Macmillan Magazines)
  The modification and control of exciton-photon interactions in semiconductors is of both fundamental and practical interest, being of direct relevance to the design of improved light-emitting diodes, photodetectors and lasers. In a semiconductor microcavity, the confined electromagnetic field modifies the optical transitions of the material. Two distinct types of interaction are possible: weak and strong coupling. In the former perturbative regime, the spectral and spatial distribution of the emission is modified but exciton dynamics are little altered. In the latter case, however, mixing of exciton and photon states occurs leading to strongly modified dynamics. Both types of effect were obsd. in planar microcavity structures in inorg. semiconductor quantum wells and bulk layers. But org. semiconductor microcavities were studied only in the weak-coupling regime. An org. semiconductor microcavity that operates in the strong-coupling regime is reported. Characteristic mixing is seen of the exciton and photon modes (anti-crossing), and a room-temp. vacuum Rabi splitting (an indicator of interaction strength) that is an order of magnitude larger than the previously reported highest values for inorg. semiconductors. The results may lead to new structures and device concepts incorporating hybrid states of org. and inorg. excitons, and suggest that polariton lasing may be possible.
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17. 17
  Ebbesen, T. W. Hybrid light-matter states in molecular and material science. Acc. Chem. Res. 2016, 49, 2403– 2412, DOI: 10.1021/acs.accounts.6b00295
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  17
  Hybrid Light-Matter States in a Molecular and Material Science Perspective
  Ebbesen, Thomas W.
  Accounts of Chemical Research (2016), 49 (11), 2403-2412CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
  A review. The notion that light and matter states can be hybridized the way s and p orbitals are mixed is a concept that is not familiar to most chemists and material scientists. Yet it has much potential for mol. and material sciences that is just beginning to be explored. For instance, it has already been demonstrated that the rate and yield of chem. reactions can be modified and that the cond. of org. semiconductors and nonradiative energy transfer can be enhanced through the hybridization of electronic transitions. The hybridization is not limited to electronic transitions; it can be applied for instance to vibrational transitions to selectively perturb a given bond, opening new possibilities to change the chem. reactivity landscape and to use it as a tool in (bio)mol. science and spectroscopy. Such results are not only the consequence of the new eigenstates and energies generated by the hybridization. The hybrid light-matter states also have unusual properties: they can be delocalized over a very large no. of mols. (up to ca. 105), and they become dispersive or momentum-sensitive. Importantly, the hybridization occurs even in the absence of light because it is the zero-point energies of the mol. and optical transitions that generate the new light-matter states. The present work is not a review but rather an Account from the author's point of view that first introduces the reader to the underlying concepts and details of the features of hybrid light-matter states. It is shown that light-matter hybridization is quite easy to achieve: all that is needed is to place mols. or a material in a resonant optical cavity (e.g., between two parallel mirrors) under the right conditions. For vibrational strong coupling, microfluidic IR cells can be used to study the consequences for chem. in the liq. phase. Examples of modified properties are given to demonstrate the full potential for the mol. and material sciences. Finally an outlook of future directions for this emerging subject is given.
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18. 18
  Orgiu, E.; George, J.; Hutchison, J. A.; Devaux, E.; Dayen, J. F.; Doudin, B.; Stellacci, F.; Genet, C.; Schachenmayer, J.; Genes, C.; Pupillo, G.; Samori, P.; Ebbesen, T. W. Conductivity in organic semiconductors hybridized with the vacuum field. Nat. Mater. 2015, 14, 1123– 1129, DOI: 10.1038/nmat4392
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  Conductivity in organic semiconductors hybridized with the vacuum field
  Orgiu, E.; George, J.; Hutchison, J. A.; Devaux, E.; Dayen, J. F.; Doudin, B.; Stellacci, F.; Genet, C.; Schachenmayer, J.; Genes, C.; Pupillo, G.; Samori, P.; Ebbesen, T. W.
  Nature Materials (2015), 14 (11), 1123-1129CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
  Much effort over the past decades was focused on improving carrier mobility in org. thin-film transistors by optimizing the organization of the material or the device architecture. Here the authors take a different path to solving this problem, by injecting carriers into states that are hybridized to the vacuum electromagnetic field. To test this idea, org. semiconductors were strongly coupled to plasmonic modes to form coherent states that can extend over as many as 105 mols. and should thereby favor cond. Indeed the current does increase by an order of magnitude at resonance in the coupled state, reflecting mostly a change in field-effect mobility. A theor. quantum model confirms the delocalization of the wavefunctions of the hybridized states and its effect on the cond. The authors' findings illustrate the potential of engineering the vacuum electromagnetic environment to modify and to improve properties of materials.
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19. 19
  Feist, J.; García-Vidal, F. J. Extraordinary exciton conductance induced by strong coupling. Phys. Rev. Lett. 2015, 114, 196402, DOI: 10.1103/PhysRevLett.114.196402
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  Extraordinary exciton conductance induced by strong coupling
  Feist, Johannes; Garcia-Vidal, Francisco J.
  Physical Review Letters (2015), 114 (19), 196402/1-196402/5CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
  We demonstrate that exciton conductance in org. materials can be enhanced by several orders of magnitude when the mols. are strongly coupled to an electromagnetic mode. Using a 1D model system, we show how the formation of a collective polaritonic mode allows excitons to bypass the disordered array of mols. and jump directly from one end of the structure to the other. This finding could have important implications in the fields of exciton transistors, heat transport, photosynthesis, and biol. systems in which exciton transport plays a key role.
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20. 20
  Schachenmayer, J.; Genes, C.; Tignone, E.; Pupillo, G. Cavity-enhanced transport of excitons. Phys. Rev. Lett. 2015, 114, 196403, DOI: 10.1103/PhysRevLett.114.196403
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  Cavity-enhanced transport of excitons
  Schachenmayer, Johannes; Genes, Claudiu; Tignone, Edoardo; Pupillo, Guido
  Physical Review Letters (2015), 114 (19), 196403/1-196403/6CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
  We show that exciton-type transport in certain materials can be dramatically modified by their inclusion in an optical cavity: the modification of the electromagnetic vacuum mode structure introduced by the cavity leads to transport via delocalized polariton modes rather than through tunneling processes in the material itself. This can help overcome exponential suppression of transmission properties as a function of the system size in the case of disorder and other imperfections. We exemplify massive improvement of transmission for excitonic wave packets through a cavity, as well as enhancement of steady-state exciton currents under incoherent pumping. These results may have implications for expts. of exciton transport in disordered org. materials. We propose that the basic phenomena can be obsd. in quantum simulators made of Rydberg atoms, cold mols. in optical lattices, as well as in expts. with trapped ions.
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21. 21
  Schlawin, F.; Cavalleri, A.; Jaksch, D. Cavity-mediated electron-photon superconductivity. Phys. Rev. Lett. 2019, 122, 133602, DOI: 10.1103/PhysRevLett.122.133602
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  Cavity-Mediated Electron-Photon Superconductivity
  Schlawin, Frank; Cavalleri, Andrea; Jaksch, Dieter
  Physical Review Letters (2019), 122 (13), 133602CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)
  A review. We investigate electron paring in a two-dimensional electron system mediated by vacuum fluctuations inside a nanoplasmonic terahertz cavity. We show that the structured cavity vacuum can induce long-range attractive interactions between current fluctuations which lead to pairing in generic materials with crit. temps. in the low-kelvin regime for realistic parameters. The induced state is a pair-d. wave superconductor which can show a transition from a fully gapped to a partially gapped phase-akin to the pseudogap phase in high-Tc superconductors. Our findings provide a promising tool for engineering intrinsic electron interactions in two-dimensional materials.
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22. 22
  Coles, D. M.; Somaschi, N.; Michetti, P.; Clark, C.; Lagoudakis, P. G.; Savvidis, P. G.; Lidzey, D. G. Polariton-mediated energy transfer between organic dyes in a strongly coupled optical microcavity. Nat. Mater. 2014, 13, 712– 719, DOI: 10.1038/nmat3950
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  Polariton-mediated energy transfer between organic dyes in a strongly coupled optical microcavity
  Coles, David M.; Somaschi, Niccolo; Michetti, Paolo; Clark, Caspar; Lagoudakis, Pavlos G.; Savvidis, Pavlos G.; Lidzey, David G.
  Nature Materials (2014), 13 (7), 712-719CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
  Strongly coupled optical microcavities contg. different exciton states permit the creation of hybrid-polariton modes that can be described in terms of a linear admixt. of cavity-photon and the constituent excitons. Such hybrid states were predicted to have optical properties that are different from their constituent parts, making them a test bed for the exploration of light-matter coupling. Here, we use strong coupling in an optical microcavity to mix the electronic transitions of 2 J-aggregated mol. dyes and use both non-resonant photoluminescence emission and photoluminescence excitation spectroscopy to show that hybrid-polariton states act as an efficient and ultrafast energy-transfer pathway between the 2 exciton states. We argue that this type of structure may act as a model system to study energy-transfer processes in biol. light-harvesting complexes.
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23. 23
  Zhong, X.; Chervy, T.; Wang, S.; George, J.; Thomas, A.; Hutchison, J. A.; Devaux, E.; Genet, C.; Ebbesen, T. W. Non-radiative energy transfer mediated by hybrid light-matter states. Angew. Chem., Int. Ed. 2016, 55, 6202, DOI: 10.1002/anie.201600428
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  Non-Radiative Energy Transfer Mediated by Hybrid Light-Matter States
  Zhong, Xiaolan; Chervy, Thibault; Wang, Shaojun; George, Jino; Thomas, Anoop; Hutchison, James A.; Devaux, Eloise; Genet, Cyriaque; Ebbesen, Thomas W.
  Angewandte Chemie, International Edition (2016), 55 (21), 6202-6206CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Direct evidence is presented of enhanced nonradiative energy transfer between 2 J-aggregated cyanine dyes strongly coupled to the vacuum field of a cavity. Excitation spectroscopy and fs pump-probe measurements show that the energy transfer is highly efficient when both the donor and acceptor form light-matter hybrid states with the vacuum field. The rate of energy transfer is increased by a factor of 7 under those conditions as compared to the normal situation outside the cavity, with a corresponding effect on the energy transfer efficiency. The delocalized hybrid states connect the donor and acceptor mols. and clearly play the role of a bridge to enhance the rate of energy transfer. This finding has fundamental implications for coherent energy transport and light-energy harvesting.
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24. 24
  Zhong, X.; Chervy, T.; Zhang, L.; Thomas, A.; George, J.; Genet, C.; Hutchison, J. A.; Ebbesen, T. W. Energy transfer between spatially separated entangled molecules. Angew. Chem., Int. Ed. 2017, 56, 9034, DOI: 10.1002/anie.201703539
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  Energy Transfer between Spatially Separated Entangled Molecules
  Zhong, Xiaolan; Chervy, Thibault; Zhang, Lei; Thomas, Anoop; George, Jino; Genet, Cyriaque; Hutchison, James A.; Ebbesen, Thomas W.
  Angewandte Chemie, International Edition (2017), 56 (31), 9034-9038CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Light-matter strong coupling allows for the possibility of entangling the wave functions of different mols. through the light field. We hereby present direct evidence of non-radiative energy transfer well beyond the Foerster limit for spatially sepd. donor and acceptor cyanine dyes strongly coupled to a cavity. The transient dynamics and the static spectra show an energy transfer efficiency approaching 37% for donor-acceptor distances ≥100 nm. In such systems, the energy transfer process becomes independent of distance as long as the coupling strength is maintained. This is consistent with the entangled and delocalized nature of the polaritonic states.
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25. 25
  Du, M.; Martínez-Martínez, M. A.; Ribeiro, R. F.; Hu, Z.; Menon, V. M.; Yuen-Zhou, J. Theory for polariton-assisted remote energy transfer. Chem. Sci. 2018, 9, 6659– 6669, DOI: 10.1039/C8SC00171E
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  Theory for polariton-assisted remote energy transfer
  Du, Matthew; Martinez-Martinez, Luis A.; Ribeiro, Raphael F.; Hu, Zixuan; Menon, Vinod M.; Yuen-Zhou, Joel
  Chemical Science (2018), 9 (32), 6659-6669CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
  Strong-coupling between light and matter produces hybridized states (polaritons) whose delocalization and electromagnetic character allow for novel modifications in spectroscopy and chem. reactivity of mol. systems. Recent expts. have demonstrated remarkable distance-independent long-range energy transfer between mols. strongly coupled to optical microcavity modes. To shed light on the mechanism of this phenomenon, we present the first comprehensive theory of polariton-assisted remote energy transfer (PARET) based on strong-coupling of donor and/or acceptor chromophores to surface plasmons. Application of our theory demonstrates that PARET up to a micron is indeed possible. In particular, we report two regimes for PARET: in one case, strong-coupling to a single type of chromophore leads to transfer mediated largely by surface plasmons while in the other case, strong-coupling to both types of chromophores creates energy transfer pathways mediated by vibrational relaxation. Importantly, we highlight conditions under which coherence enhances or deteriorates these processes. For instance, while exclusive strong-coupling to donors can enhance transfer to acceptors, the reverse turns out not to be true. However, strong-coupling to acceptors can shift energy levels in a way that transfer from acceptors to donors can occur, thus yielding a chromophore role-reversal or "carnival effect". This theor. study demonstrates the potential for confined electromagnetic fields to control and mediate PARET, thus opening doors to the design of remote mesoscale interactions between mol. systems.
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26. 26
  Sáez-Blázquez, R.; Feist, J.; Fernández-Domínguez, A. I.; García-Vidal, F. J. Organic polaritons enable local vibrations to drive long-range energy transfer. Phys. Rev. B: Condens. Matter Mater. Phys. 2018, 97, 241407R, DOI: 10.1103/PhysRevB.97.241407
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27. 27
  Gonzalez-Ballestero, C.; Feist, J.; Moreno, E.; Garcia-Vidal, F. J. Harvesting excitons through plasmonic strong coupling. Phys. Rev. B: Condens. Matter Mater. Phys. 2015, 92, 121402R, DOI: 10.1103/PhysRevB.92.121402
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  Harvesting excitons through plasmonic strong coupling
  Gonzalez-Ballestero, Carlos; Feist, Johannes; Moreno, Esteban; Garcia-Vidal, Francisco J.
  Physical Review B: Condensed Matter and Materials Physics (2015), 92 (12), 121402/1-121402/5CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
  Exciton harvesting is demonstrated in an ensemble of quantum emitters coupled to localized surface plasmons. When the interaction between emitters and the dipole mode of a metallic nanosphere reaches the strong-coupling regime, the exciton conductance is greatly increased. The spatial map of the conductance matches the plasmon field intensity profile, which indicates that transport properties can be tuned by adequately tailoring the field of the plasmonic resonance. Under strong coupling, we find that pure dephasing can have detrimental or beneficial effects on the conductance, depending on the effective no. of participating emitters. Finally, we show that the exciton transport in the strong-coupling regime occurs on an ultrafast time scale given by the inverse Rabi splitting (∼10 fs), which is orders of magnitude faster than transport through direct hopping between the emitters.
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28. 28
  García-Vidal, F. J.; Feist, J. Long-distance operator for energy transfer. Science 2017, 357, 1357– 1358, DOI: 10.1126/science.aao4268
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  Long-distance operator for energy transfer
  Garcia-Vidal, Francisco J.; Feist, Johannes
  Science (Washington, DC, United States) (2017), 357 (6358), 1357-1358CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
  There is no expanded citation for this reference.
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29. 29
  Wientjes, E.; Renger, J.; Curto, A. G.; Cogdell, R.; van Hulst, N. F. Strong antenna-enhanced fluorescence of a single light-harvesting complex shows photon antibunching. Nat. Commun. 2014, 5, 4236, DOI: 10.1038/ncomms5236
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  Strong antenna-enhanced fluorescence of a single light-harvesting complex shows photon antibunching
  Wientjes, Emilie; Renger, Jan; Curto, Alberto G.; Cogdell, Richard; van Hulst, Niek F.
  Nature Communications (2014), 5 (), 4236CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)
  The nature of the highly efficient energy transfer in photosynthetic light-harvesting complexes is a subject of intense research. Unfortunately, the low fluorescence efficiency and limited photostability hampers the study of individual light-harvesting complexes at ambient conditions. Here, we demonstrate an over 500-fold fluorescence enhancement of light-harvesting complex 2 (LH2) at the single-mol. level by coupling to a gold nanoantenna. The resonant antenna produces an excitation enhancement of circa 100 times and a fluorescence lifetime shortening to ∼\n20 ps. The radiative rate enhancement results in a 5.5-fold-improved fluorescence quantum efficiency. Exploiting the unique brightness, we have recorded the first photon antibunching of a single light-harvesting complex under ambient conditions, showing that the 27 bacteriochlorophylls coordinated by LH2 act as a non-classical single-photon emitter. The presented bright antenna-enhanced LH2 emission is a highly promising system to study energy transfer and the role of quantum coherence at the level of single complexes.
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30. 30
  Wientjes, E.; Renger, J.; Cogdell, R.; van Hulst, N. F. Pushing the photon limit: nanoantennas increase maximal photon stream and total photon number. J. Phys. Chem. Lett. 2016, 7, 1604– 1609, DOI: 10.1021/acs.jpclett.6b00491
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  30
  Pushing the Photon Limit: Nanoantennas Increase Maximal Photon Stream and Total Photon Number
  Wientjes, Emilie; Renger, Jan; Cogdell, Richard; van Hulst, Niek F.
  Journal of Physical Chemistry Letters (2016), 7 (9), 1604-1609CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
  Nanoantennas are known for their effective role in fluorescence enhancement, both in excitation and emission. Enhancements of 3-4 orders of magnitude were reported. Yet in practice, the photon emission is limited by satn. due to the time that a mol. spends in singlet and esp. triplet excited states. The max. photon stream restricts the attainable enhancement. The total no. of photons emitted is limited by photobleaching. The limited brightness and observation time are a drawback for applications, esp. in biol. This photon limit is challenged, showing that nanoantennas can actually increase both satn. intensity and photostability. So far, this limit-shifting role of nanoantennas has hardly been explored. Single light-harvesting complexes, under satg. excitation conditions, show >50-fold antenna-enhanced photon emission stream, with 10-fold more total photons, ≤108 detected photons, before photobleaching. This work shows yet another facet of the great potential of nanoantennas in the world of single-mol. biol.
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31. 31
  Tsargorodska, A.; Cartron, M. L.; Vasilev, C.; Kodali, G.; Mass, O. A.; Baumberg, J. J.; Dutton, P. L.; Hunter, C. N.; Törmä, P.; Leggett, G. J. Strong coupling of localized surface plasmons to excitons in light-harvesting complexes. Nano Lett. 2016, 16, 6850– 6856, DOI: 10.1021/acs.nanolett.6b02661
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  Strong Coupling of Localized Surface Plasmons to Excitons in Light-Harvesting Complexes
  Tsargorodska, Anna; Cartron, Michael L.; Vasilev, Cvetelin; Kodali, Goutham; Mass, Olga A.; Baumberg, Jeremy J.; Dutton, P. Leslie; Hunter, C. Neil; Torma, Paivi; Leggett, Graham J.
  Nano Letters (2016), 16 (11), 6850-6856CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
  Gold nanostructure arrays exhibit surface plasmon resonances that split after attaching light harvesting complexes 1 and 2 (LH1 and LH2) from purple bacteria. The splitting is attributed to strong coupling between the localized surface plasmon resonances and excitons in the light-harvesting complexes. Wild-type and mutant LH1 and LH2 from Rhodobacter sphaeroides contg. different carotenoids yield different splitting energies, demonstrating that the coupling mechanism is sensitive to the electronic states in the light harvesting complexes. Plasmon-exciton coupling models reveal different coupling strengths depending on the mol. organization and the protein coverage, consistent with strong coupling. Strong coupling was also obsd. for self-assembling polypeptide maquettes that contain only chlorins. However, it is not obsd. for monolayers of bacteriochlorophyll, indicating that strong plasmon-exciton coupling is sensitive to the specific presentation of the pigment mols.
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32. 32
  Caprasecca, S.; Corni, S.; Mennucci, B. Shaping excitons in light-harvesting proteins through nanoplasmonics. Chem. Sci. 2018, 9, 6219– 6227, DOI: 10.1039/C8SC01162A
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  Shaping excitons in light-harvesting proteins through nanoplasmonics
  Caprasecca, Stefano; Corni, Stefano; Mennucci, Benedetta
  Chemical Science (2018), 9 (29), 6219-6227CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
  Nanoplasmonics has been used to enhance mol. spectroscopic signals, with exquisite spatial resoln. down to the sub-mol. scale. By means of a rigorous, state-of-the-art multiscale model based on a quantum chem. description, here we show that optimally tuned tip-shaped metal nanoparticles can selectively excite localized regions of typically coherent systems, eventually narrowing down to probing one single pigment. The well-known major light-harvesting complex LH2 of purple bacteria has been investigated because of its unique properties, as it presents both high and weak delocalization among subclusters of pigments. This finding opens the way to the direct spectroscopic investigation of quantum-based processes, such as the quantum diffusion of the excitation among the chromophores, and their external manipulation.
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33. 33
  Coles, D. M.; Yang, Y.; Wang, Y.; Grant, R. T.; Taylor, R. A.; Saikin, S. K.; Aspuru-Guzik, A.; Lidzey, D. G.; Tang, J. K.-H.; Smith, J. M. Strong coupling between chlorosomes of photosynthetic bacteria and a confined optical cavity mode. Nat. Commun. 2014, 5, 5561, DOI: 10.1038/ncomms6561
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  Strong coupling between chlorosomes of photosynthetic bacteria and a confined optical cavity mode
  Coles, David M.; Yang, Yanshen; Wang, Yaya; Grant, Richard T.; Taylor, Robert A.; Saikin, Semion K.; Aspuru-Guzik, Alan; Lidzey, David G.; Tang, Joseph Kuo-Hsiang; Smith, Jason M.
  Nature Communications (2014), 5 (), 5561CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)
  Strong exciton-photon coupling is the result of a reversible exchange of energy between an excited state and a confined optical field. This results in the formation of polariton states that have energies different from the exciton and photon. We demonstrate strong exciton-photon coupling between light-harvesting complexes and a confined optical mode within a metallic optical microcavity. The energetic anti-crossing between the exciton and photon dispersions characteristic of strong coupling is obsd. in reflectivity and transmission with a Rabi splitting energy on the order of 150 meV, which corresponds to about 1000 chlorosomes coherently coupled to the cavity mode. We believe that the strong coupling regime presents an opportunity to modify the energy transfer pathways within photosynthetic organisms without modification of the mol. structure.
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34. 34
  Coles, D.; Flatten, L. C.; Sydney, T.; Hounslow, E.; Saikin, S. K.; Aspuru-Guzik, A.; Vedral, V.; Tang, J. K. H.; Taylor, R. A.; Smith, J. M.; Lidzey, D. G. A nanophotonic structure containing living photosynthetic bacteria. Small 2017, 13, 1701777, DOI: 10.1002/smll.201701777
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  Generalized theory of relaxation
  Bloch, F.
  Physical Review (1957), 105 (), 1206-22CODEN: PHRVAO; ISSN:0031-899X.
  cf. C.A. 47, 7307i. A further generalization is given of the earlier theory.
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36. 36
  Redfield, A. G. On the theory of relaxation processes. IBM J. Res. Dev. 1957, 1, 19, DOI: 10.1147/rd.11.0019
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37. 37
  Ritz, T.; Park, S.; Schulten, K. Kinetics of excitation migration and trapping in the photosynthetic unit of purple bacteria. J. Phys. Chem. B 2001, 105, 8259– 8267, DOI: 10.1021/jp011032r
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  Kinetics of Excitation Migration and Trapping in the Photosynthetic Unit of Purple Bacteria
  Ritz, Thorsten; Park, Sanghyun; Schulten, Klaus
  Journal of Physical Chemistry B (2001), 105 (34), 8259-8267CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)
  Purple bacteria have developed an efficient app. to harvest sunlight. The app. consists of up to four types of pigment-protein complexes: (i) the photosynthetic reaction center surrounded by (ii) the light-harvesting complex LH1, (iii) antenna complexes LH2, which are replaced under low-light conditions by (iv) antenna complexes LH3 with a higher absorption max. Following absorption of light anywhere in the app., electronic excitation is transferred between the pigment-protein complexes until it is used for the primary photoreaction in the reaction center. We calc., using F.ovrddot.orster theory, all rates for the inter-complex excitation transfer processes on the basis of the at. level structures of the pigment-protein complexes and of an effective Hamiltonian, established previously, for intracomplex excitations. The kinetics of excitation migration in the photosynthetic app. is described through a master equation which connects the calcd. transfer rates to the overall architecture of the app. For two exemplary architectures the efficiency, distribution of dissipation, and time evolution of excitation migration are detd. Pigment-protein complexes are found to form an excitation reservoir, in which excitation is spread over many chromophores rather than forming an excitation funnel in which excitation is transferred without detours from the periphery to the RC. This feature permits a high quantum yield of 83% to 89%, but also protects the app. from overheating by spreading dissipation over all complexes. Substitution of LH2 complexes by LH3 complexes or changing an architecture in which few LH2 (LH3) complexes are in contact with LH1 to an architecture in which all LH2 (LH3) complexes are in contact with LH1 increases the quantum yield up to 94% and decreases the degree to which dissipation is evenly distributed.
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38. 38
  Caycedo-Soler, F.; Schroeder, C. A.; Autenrieth, C.; Pick, A.; Ghosh, R.; Huelga, S. F.; Plenio, M. B. Quantum redirection of antenna absorption to photosynthetic reaction centers. J. Phys. Chem. Lett. 2017, 8, 6015– 6021, DOI: 10.1021/acs.jpclett.7b02714
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  Quantum redirection of antenna absorption to photosynthetic reaction centers
  Caycedo-Soler, Felipe; Schroeder, Christopher A.; Autenrieth, Caroline; Pick, Arne; Ghosh, Robin; Huelga, Susana F.; Plenio, Martin B.
  Journal of Physical Chemistry Letters (2017), 8 (24), 6015-6021CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
  The early steps of photosynthesis involve the photoexcitation of reaction centers (RCs) and light-harvesting (LH) units. Here, we show that the historically overlooked excitonic delocalization across RC and LH pigments results in a redistribution of absorption amplitudes that benefits the absorption cross-section of the optical bands assocd. with the RC of several species. While we proved that this redistribution is robust to the microscopic details of the dephasing between these units in the purple bacterium, Rhodospirillum rubrum, we were able to show that the redistribution witnessed a more fragile, but persistent, coherent population dynamics which directed excitations from the LH toward the RC units under incoherent illumination and physiol. conditions. Even though the redirection did not seem to affect importantly the overall efficiency in photosynthesis, stochastic optimization allowed us to delineate clear guidelines and develop simple analytic expressions in order to amplify the coherent redirection in artificial nanostructures.
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39. 39
  McDermott, G.; Prince, S. M.; Freer, A. A.; Hawthornthwaite-Lawless, A. M.; Papiz, M. Z.; Cogdell, R. J.; Isaacs, N. W. Crystal structure of an integral membrane light-harvesting complex from photosynthetic bacteria. Nature 1995, 374, 517– 521, DOI: 10.1038/374517a0
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  Crystal structure of an integral membrane light-harvesting complex from photosynthetic bacteria
  McDermott, G.; Prince, S. M.; Freer, A. A.; Hawthornthwaite-Lawless, A. M.; Papiz, M. Z.; Cogdell, R. J.; Isaacs, N. W.
  Nature (London) (1995), 374 (6522), 517-21CODEN: NATUAS; ISSN:0028-0836. (Macmillan Magazines)
  The crystal structure of the light-harvesting antenna complex (LH2) from Rhodopseudomonas acidophila strain 10050 shows that the active assembly consists of two concentric cylinders of helical protein subunits which enclose the pigment mols. Eighteen bacteriochlorophyll a mols. sandwiched between the helixes form a continuous overlapping ring, and a further nine are positioned between the outer helixes with the bacteriochlorin rings perpendicular to the transmembrane helix axis. There is an elegant intertwining of the bacteriochlorophyll phytol chains with carotenoid, which spans the complex.
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40. 40
  Cupellini, L.; Jurinovich, S.; Campetella, M.; Caprasecca, S.; Guido, C. A.; Kelly, S. M.; Gardiner, A. T.; Cogdell, R.; Mennucci, B. An ab initio description of the excitonic properties of LH2 and their temperature dependence. J. Phys. Chem. B 2016, 120, 11348– 11359, DOI: 10.1021/acs.jpcb.6b06585
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  40
  An ab initio description of the excitonic properties of LH2 and their temperature dependence
  Cupellini, Lorenzo; Jurinovich, Sandro; Campetella, Marco; Caprasecca, Stefano; Guido, Ciro A.; Kelly, Sharon M.; Gardiner, Alastair T.; Cogdell, Richard; Mennucci, Benedetta
  Journal of Physical Chemistry B (2016), 120 (44), 11348-11359CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
  The spectroscopic properties of light-harvesting (LH) antennae in photosynthetic organisms represent a fingerprint that is unique for each specific pigment-protein complex. Because of that, spectroscopic observations are generally combined with structural data from x-ray crystallog. to obtain an indirect representation of the excitonic properties of the system. Here, an alternative strategy is presented which goes beyond this empirical approach and introduces an ab initio computational description of both structural and electronic properties and their dependence on the temp. The strategy was applied to the peripheral light-harvesting antenna complex (LH2) present in purple bacteria. By comparing this model with the one based on the crystal structure, a detailed, mol. level explanation of the absorption and CD spectra and their temp. dependence was achieved. The agreement obtained with the expts. at both low and room temp. lays the groundwork for an atomistic understanding of the excitation dynamics in the LH2 system.
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41. 41
  Caycedo-Soler, F.; Lim, F.; Oviedo-Casado, S.; van Hulst, N. F.; Huelga, S. F.; Plenio, M. B. Theory of excitonic delocalization for robust vibronic dynamics in LH2. J. Phys. Chem. Lett. 2018, 9, 3446– 3453, DOI: 10.1021/acs.jpclett.8b00933
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  41
  Theory of Excitonic Delocalization for Robust Vibronic Dynamics in LH2
  Caycedo-Soler, Felipe; Lim, James; Oviedo-Casado, Santiago; van Hulst, Niek F.; Huelga, Susana F.; Plenio, Martin B.
  Journal of Physical Chemistry Letters (2018), 9 (12), 3446-3453CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
  Nonlinear spectroscopy has revealed long-lasting oscillations in the optical response of a variety of photosynthetic complexes. Different theor. models that involve the coherent coupling of electronic (excitonic) or electronic-vibrational (vibronic) degrees of freedom have been put forward to explain these observations. The ensuing debate concerning the relevance of either mechanism may have obscured their complementarity. To illustrate this balance, we quantify how the excitonic delocalization in the LH2 unit of Rhodopseudomonas acidophila purple bacterium leads to correlations of excitonic energy fluctuations, relevant coherent vibronic coupling, and importantly, a decrease in the excitonic dephasing rates. Combining these effects, we identify a feasible origin for the long-lasting oscillations obsd. in fluorescent traces from time-delayed two-pulse single-mol. expts. performed on this photosynthetic complex and use this approach to discuss the role of this complementarity in other photosynthetic systems.
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42. 42
  Zazubovich, V.; Tibe, I.; Small, G. J. Bacteriochlorophyll a Franck-Condon Factors for the S0→S1(Qy) Transition. J. Phys. Chem. B 2001, 105, 12410– 12417, DOI: 10.1021/jp012804m
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  42
  Bacteriochlorophyll a Franck-Condon Factors for the S0 → S1(Qy) Transition
  Zazubovich, V.; Tibe, I.; Small, G. J.
  Journal of Physical Chemistry B (2001), 105 (49), 12410-12417CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)
  Pseudovibronic satellite hole-burning spectroscopy of bacteriochlorophyll a (BChl a) in two glasses at 5 K was used to det. the Franck-Condon (FC) factors for 56 one-quantum (0 → 1) vibrational transitions that lie between 160 and 1600 cm-1. As in the case of Chl a (Pieper, J.; et al. J. Phys. Chem. B 1999, 103, 2319), the FC factors are small, ranging between 0.05 and 0.0007 (uncertainty ≈ ±20%). The FC factors, together with the exptl. detd. inhomogeneous site excitation distribution function for the zero-phonon line and linear electron-phonon coupling parameters, account well for the S0 → Qy absorption spectra. Thus, the FC factors are accurate enough to be used in quantum mech. calcns. of excitation energy transfer rates in photosynthetic antenna complexes (with their intrinsic structural heterogeneity) exhibiting excitonic coupling that ranges between weak and strong. The BChl a FC factors detd. by hole burning are compared with those obtained by fluorescence line narrowing spectroscopy (Wendling, M.; et al. J. Phys. Chem. B 2000, 104, 5825). The latter, which are about a factor of 5 smaller than those detd. by hole burning, are too small to account for the vibronic contribution to the S0 → Qy absorption spectrum. The discrepancy between the two sets of FC factors is discussed.
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43. 43
  De Caro, C.; Visschers, R. W.; van Grondelle, R.; Völker, S. Inter- and intraband energy transfer in LH2-antenna complexes of purple bacteria. A fluorescence line-narrowing and hole-burning study. J. Phys. Chem. 1994, 98, 10584– 10590, DOI: 10.1021/j100092a032
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  Inter- and Intraband Energy Transfer in LH2-Antenna Complexes of Purple Bacteria. A Fluorescence Line-Narrowing and Hole-Burning Study
  De Caro, C.; Visschers, R. W.; van Grondelle, R.; Voelker, S.
  Journal of Physical Chemistry (1994), 98 (41), 10584-90CODEN: JPCHAX; ISSN:0022-3654.
  High-resoln. site-selection fluorescence- and hole-burning spectroscopy were used to study energy transfer in two LH2 light-harvesting complexes of purple bacteria: the B800-850 complex of isolated Rhodobacter sphaeroides and the B800-820 complex of Rhodopseudomonas acidophila, at 1.2 K. Fluorescence spectra, hole widths, and hole depths were measured as a function of excitation wavelength λexc within the B800 band. For λexc ≥ 798 nm, fluorescence line-narrowing is obsd. and the energy-transfer times (τ = 2.5 and 2.0 ps for B800-850 and B800-820, resp.) are independent of λexc. In this spectral region only interband B800 → B850 (B820) energy transfer takes place. For 780 nm ≤ λexc ≤ 798 nm, the fluorescence bands are broad and the transfer time, obtained from hole widths extrapolated to zero burning-fluence d., decreases toward the blue side of B800. In this wavelength region competition occurs between B800 → B850 (B820) and B800 → B800 "downhill" energy transfer. For λexc ≤ 780 nm, the broad fluorescence bands, with maxima at λem ∼805 nm, become independent of λexc and intraband B800 → B800 transfer combined with excited-state vibrational relaxation are the dominant processes. The spectral distribution of the most-red absorbing pigments within the B800 band, which transfer energy exclusively from B800to B850 (B820), was detd. from the depth of the hole vs. λexc. The results indicate that one-third of the B800 pigments transfer their energy only to B850 (B820), from which it is concluded that the minimal functional LH2-unit consists of at least three B800 pigments and six B850 pigments, in addn. to carotenoids.
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44. 44
  Sauer, K.; Cogdell, R. J.; Prince, S. M.; Freer, A.; Isaacs, N. W.; Scheer, H. Structure-based calculations of the optical spectra of the LH2 bacteriochlorophyll-protein complex from Rhodopseudomonas acidophila. Photochem. Photobiol. 1996, 64, 564– 576, DOI: 10.1111/j.1751-1097.1996.tb03106.x
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  Structure-based calculations of the optical spectra of the LH2 bacteriochlorophyll-protein complex from Rhodopseudomonas acidophila
  Sauer, Kenneth; Cogdell, Richard J.; Prince, Steve M.; Freer, Andy; Isaacs, Neil W.; Scheer, Hugo
  Photochemistry and Photobiology (1996), 64 (3), 564-576CODEN: PHCBAP; ISSN:0031-8655. (American Society for Photobiology)
  The mol. structure of the light-harvesting complex 2 (LH2) bacteriochlorophyll-protein antenna complex from the purple non-sulfur photosynthetic bacterium R. acidophila, strain 10050 provides the positions and orientations of the 27 bacteriochlorophyll (BChl) mols. in the complex. Our structure-based model calcns. of the distinctive optical properties (absorption, CD, polarization) of LH2 in the near-IR region use a point-monopole approxn. to represent the BChl Qy transition moment. The results of the calcns. support the assignment of the ring of 18 closely coupled BChl to B850 (BChl absorbing at 850 nm) and the larger diam., parallel ring of 9 weakly coupled BChl to B800. All of the significantly allowed transitions in the near-IR-are calcd. to be perpendicular to the C9 symmetry axis, in agreement with polarization studies of this membrane-assocd. complex. To match the absorption maxima of the B800 and B850 components using a relative permittivity (dielec. const.) of 2.1, we assign different site energies (12,500 and 12,260 cm-1, resp.) for the Qy transitions of the resp. BChl in their protein binding sites. Excitonic coupling is particularly strong among the set of B850 chromophores, with pairwise interaction energies nearly 300 cm-1 between nearest neighbors, comparable with the exptl. absorption bandwidths at room temp. These strong interactions, for the full set of 18 B850 chromophores, result in an excitonic manifold that is 1200 cm-1 wide. Some of the upper excitonic states should result in weak absorption and perhaps stronger CD features. These predictions from the calcns. await exptl. verification.
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45. 45
  Tretiak, S.; Middleton, C.; Chernyak, V.; Mukamel, S. Bacteriochlorophyll and carotenoid excitonic couplings in the LH2 system of purple bacteria. J. Phys. Chem. B 2000, 104, 9540– 9553, DOI: 10.1021/jp001585m
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  Bacteriochlorophyll and carotenoid excitonic couplings in the LH2 system of purple bacteria
  Tretiak, Sergei; Middleton, Chris; Chernyak, Vladimir; Mukamel, Shaul
  Journal of Physical Chemistry B (2000), 104 (40), 9540-9553CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)
  An effective Frenkel-exciton Hamiltonian for the entire LH2 photosynthetic complex (B800, B850, and carotenoids) from Rhodospirillum molischianum is calcd. by combining the crystal structure with the Collective Electronic Oscillators (CEO) algorithm for optical response. Electronic couplings among all pigments are computed for the isolated complex and in a dielec. medium, whereby the protein environment contributions are incorporated using the Self-Consistent Reaction Field approach. The absorption spectra are analyzed by computing the electronic structure of the bacteriochlorophylls and carotenoids forming the complex. Interchromophore electronic couplings are then calcd. using both a spectroscopic approach, which derives couplings from Davydov's splittings in the dimer spectra, and an electrostatic approach, which directly computes the Coulomb integrals between transition densities of each chromophore. A comparison of the couplings obtained using these two methods allows for the sepn. of the electrostatic (F.ovrddot.orster) and electron exchange (Dexter) contributions. The significant impact of solvation on intermol. interactions reflects the need for properly incorporating the protein environment in accurate computations of electronic couplings. The F.ovrddot.orster incoherent energy transfer rates among the weakly coupled B800-B800, B800-B850, Lyc-B850, and Lyc-B850 mols. are calcd., and the effects of the dielec. medium on the LH2 light-harvesting function are analyzed and discussed.
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46. 46
  Linnanto, J.; Korppi-Tommola, J. E. I.; Helenius, V. M. Electronic States, Absorption spectrum and circular dichroism spectrum of the photosynthetic bacterial LH2 antenna of Rhodopseudomonas acidophilas predicted by exciton theory and semiempirical calculations. J. Phys. Chem. B 1999, 103, 8739– 8750, DOI: 10.1021/jp9848344
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  46
  Electronic states, absorption spectrum and circular dichroism spectrum of the photosynthetic bacterial LH2 antenna of Rhodopseudomonas acidophila as predicted by exciton theory and semiempirical calculations
  Linnanto, J.; Korppi-Tommola, J. E. I.; Helenius, V. M.
  Journal of Physical Chemistry B (1999), 103 (41), 8739-8750CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)
  A new approach that uses a combination of semiempirical CI method and exciton theory to calc. electronic energies, eigenstates, absorption spectrum and CD (CD) spectrum of the LH2 antenna of Rhodopseudomonas acidophila is introduced. A statistical simulation that uses exptl. homogeneous line widths was used to account for the inhomogeneous line width of the obsd. spectrum. Including the effect of orbital overlap of the close-lying pigments of the B850 ring and the effect of the pigment protein interaction in the B800 ring allowed a successful simulation of the exptl. absorption and CD spectra of the antenna at room temp. Two exptl. parameters, the transition energy and the magnitude of the transition dipole moment of monomeric bacteriochlorophyll a (Bchl a), were used in the calcn. The dielec. const. of the protein matrix was taken as 2.1 [ε0]. The questions of localization lengths of the excitonic states and the energy transfer mechanism between the B800 and the B850 rings are discussed in light of the results obtained.
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47. 47
  van Oijen, A. M.; Ketelaars, M.; Köhler, J.; Aartsma, T. J.; Schmidt, J. Unraveling the electronic structure of individual photosynthetic pigment-protein complexes. Science 1999, 285, 400– 402, DOI: 10.1126/science.285.5426.400
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  Unraveling the electronic structure of individual photosynthetic pigment-protein complexes
  Van Oijen, Antoine M.; Ketelaars, Martijn; Kohler, Jirgen; Aartsma, Thijs J.; Schmidt, Jan
  Science (Washington, D. C.) (1999), 285 (5426), 400-402CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
  Low-temp. single-mol. spectroscopic techniques were applied to a light-harvesting pigment-protein complex (LH2) from purple photosynthetic bacteria. The properties of the electronically excited states of the two circular assemblies (B800 and B850) of bacteriochlorophyll a (BChl a) pigment mols. in the individual complexes were revealed, without ensemble averaging. The results show that the excited states of the B800 ring of pigments are mainly localized on individual BChl a mols. In contrast, the absorption of a photon by the 8850 ring can be consistently described in terms of an excitation that is completely delocalized over the ring. This property may contribute to the high efficiency of energy transfer in these photosynthetic complexes.
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48. 48
  Hildner, R.; Brinks, D.; Nieder, J. B.; Cogdell, R. J.; van Hulst, N. F. Quantum coherent energy transfer over varying pathways in single light-harvesting complexes. Science 2013, 340, 1448– 1451, DOI: 10.1126/science.1235820
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  Quantum coherent energy transfer over varying pathways in single light-harvesting complexes
  Hildner, Richard; Brinks, Daan; Nieder, Jana B.; Cogdell, Richard J.; van Hulst, Niek F.
  Science (Washington, DC, United States) (2013), 340 (6139), 1448-1451CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
  The initial steps of photosynthesis comprise the absorption of sunlight by pigment-protein antenna complexes followed by rapid and highly efficient funneling of excitation energy to a reaction center. In these transport processes, signatures of unexpectedly long-lived coherences have emerged in two-dimensional ensemble spectra of various light-harvesting complexes. Here, the authors demonstrate ultrafast quantum coherent energy transfer within individual antenna complexes of a purple bacterium under physiol. conditions. They find that quantum coherences between electronically coupled energy eigenstates persist at least 400 fs and that distinct energy-transfer pathways that change with time can be identified in each complex. The data suggest that long-lived quantum coherence renders energy transfer in photosynthetic systems robust in the presence of disorder, which is a prerequisite for efficient light harvesting.
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49. 49
  Giannini, V.; Fernández-Domínguez, A. I.; Heck, S. C.; Maier, S. A. Plasmonic nanoantennas: fundamentals and their use in controlling the radiative properties of nanoemitters. Chem. Rev. 2011, 111, 3888– 3912, DOI: 10.1021/cr1002672
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  49
  Plasmonic nanoantennas: Fundamentals and their use in controlling the radiative properties of nanoemitters
  Giannini, Vincenzo; Fernandez-Dominguez, Antonio I.; Heck, Susannah C.; Maier, Stefan A.
  Chemical Reviews (Washington, DC, United States) (2011), 111 (6), 3888-3912CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
  A review.
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  Hu, S.; Khater, M.; Salas-Montiel, R.; Kratschmer, E.; Engelmann, S.; Green, W. M. J.; Weiss, S. M. Experimental realization of deep-subwavelength confinement in dielectric optical resonators. Sci. Adv. 2018, 4, eaat2355 DOI: 10.1126/sciadv.aat2355
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Cavity-Modified Exciton Dynamics in Photosynthetic Units

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