Electron−Vibrational Coupling in the Fenna−Matthews−Olson Complex of Prosthecochloris aestuarii Determined by Temperature-Dependent Absorption and Fluorescence Line-Narrowing Measurements

Wendling, M.; Pullerits, Tõnu; Przyjalgowski, Milosz; Vulto, S. I. E.; Aartsma, Thijs J.; Grondelle, van R.; Amerongen, van H.

doi:10.1021/jp000077+

Cited by 176 publications

(295 citation statements)

References 23 publications

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“…For FMO, several Franck-Condon active vibrations are found with frequencies in the range of 0 to 350 cm −1 [11,19]. Similar low-frequency phonons contribute to the observed dynamics of retinal proteins involved in vision [20,21].…”

Section: Introductionmentioning

confidence: 69%

“…The signatures of vibronic coupling in multidimensional spectroscopy have drawn great interest lately, in particular to interpret oscillatory transients observed for light-harvesting complexes [3,[8][9][10] that persist much longer than predicted electronic dephasing times [11].…”

Section: Resultsmentioning

confidence: 99%

“…For FMO, the oscillations were found to persist for hundreds of femtoseconds at ambient temperatures and even up to a few picoseconds at 77 K [10]. In contrast, the measured spectral linewidths predict electronic dephasing times at 77 K hardly exceeding 100 fs [11], owing to rapid, stochastic variations in the environment, and coherences between excitons are expected to decay roughly on this timescale. The long coherence times could be explained by correlations between the fluctuating electronic site transition energies, but these are not concordant with recent molecular dynamics simulations [12,13].…”

Section: Introductionmentioning

confidence: 84%

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Laser-Limited Signatures of Quantum Coherence

et al. 2015

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The observation of persistent oscillatory signals in multidimensional spectra of proteinpigment complexes has spurred a debate on the role of coherence-assisted electronic energy transfer as a key operating principle in photosynthesis. Vibronic coupling has recently been proposed as an explanation for the long lifetime of the observed spectral beatings. However, photosynthetic systems are inherently complicated, and tractable studies on simple molecular compounds are in demand to fully understand the underlying physics. In this work, we present measurements and calculations on a solvated molecular homodimer with clearly resolvable oscillations in the corresponding twodimensional spectra. Through analysis of the various contributions to the nonlinear response, we succeed in isolating the signal due to inter-exciton coherence. We find that while calculations predict a prolongation of this coherence due to vibronic coupling, the combination of dynamic disorder and vibrational relaxation leads to a coherence decay on a timescale comparable to the electronic dephasing time.

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Section: Introductionmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 84%

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Laser-Limited Signatures of Quantum Coherence

et al. 2015

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“…Both these properties are described by the environmental spectral function J (ω) and the transition rate W nm is proportional to J (E nm ). As typical PPC spectral functions often have (at least) one maximum at a finite frequency [21] and may exhibit sharp features due to long-lived vibrational modes in the environment, it becomes possible to tune the Hamiltonian parameters to create excitonic states with energy differences E nm at local maxima of the spectral function and thus optimise W nm . This is the basis of the phonon antenna effect.…”

mentioning

confidence: 99%

Exploiting Structured Environments for Efficient Energy Transfer: The Phonon Antenna Mechanism

Rey

Chin

Huelga

et al. 2013

J. Phys. Chem. Lett.

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A non-trivial interplay between quantum coherence and dissipative environment-driven dynamics is becoming increasingly recognised as key for efficient energy transport in photosynthetic pigment-protein complexes, and converting these biologically-inspired insights into a set of design principles that can be implemented in artificial light-harvesting systems has become an active research field. Here we identify a specific design principlethe phonon antenna -that demonstrates how inter-pigment coherence is able to modify and optimize the way that excitations spectrally sample their local environmental fluctuations. We place this principle into a broader context and furthermore we provide evidence that the Fenna-Matthews-Olson complex of green sulphur bacteria has an excitonic structure that is close to such an optimal operating point, and suggest that this general design principle might well be exploited in other biomolecular systems. Introduction.-Experimental techniques such as optical 2D Fourier Transform spectroscopy have recently begun to probe the ultrafast photophysics of energy transport in a range of pigment-protein complexes (PPCs) taken from photosynthetic green sulphur bacteria, marine algae and higher plants [1][2][3][4]. All of the key photosynthetic light reactions (photon capture, energy transport and charge generation) are carried out in PPC structures [5,6], and the often > 90% quantum efficiency with which they carry out these functions has created considerable interest in understanding and exploiting their design features for artifical solar energy applications [5,7]. Surprisingly, recent experiments have found direct evidence for long-lasting quantum coherence amongst the excitons which transport energy in these complexes. In the case of the Fenna-MatthewsOlson (FMO) complex, these coherences can persist on picosecond timescales in cryogenic conditions and are still observable at room temperatures [2,8]. Several phenomenological theories have subsequently shown that there is an optimal mixture of coherent inter-pigment energy transport and stochastic environmental noise that may lead to faster and higher-yield energy delivery in PPC architectures, suggesting that quantum effects may underpin their efficient function [9][10][11][12][13][14][15]. Microscopic investigations have also recently shown the key role of both discrete and continuous environmental fluctuation spectra in stabilising the long-lasting coherences observed in spectroscopy as well as facilitating efficient transport [16][17][18][19][20].

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“…Even a system as small as FMO has around thirty strong vibrational modes [13,14], making a full system treatment intractable. However, we argue here that only the vibrational levels that create resonant pathways through the network contribute substantially to the dynamics of energy transfer.…”

Section: A a Coherent Model For Vibration-assisted Resonancementioning

confidence: 99%

Vibration-assisted resonance in photosynthetic excitation-energy transfer

2014

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Understanding how the effectiveness of natural photosynthetic energy harvesting systems arises from the interplay between quantum coherence and environmental noise represents a significant challenge for quantum theory. Recently it has begun to be appreciated that discrete molecular vibrational modes may play an important role in the dynamics of such systems. As an alternative to computationally demanding numerical approaches, we present a microscopic mechanism by which intramolecular vibrations contribute to the efficiency and directionality of energy transfer. Excited vibrational states create resonant pathways through the system, supporting fast and efficient energy transport. Vibrational damping together with the natural downhill arrangement of molecular energy levels gives intrinsic directionality to the energy flow. Analytical and numerical results demonstrate a significant enhancement of the efficiency and directionality of energy transport that can be directly related to the existence of resonances between vibrational and excitonic levels.

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Electron−Vibrational Coupling in the Fenna−Matthews−Olson Complex of Prosthecochloris aestuarii Determined by Temperature-Dependent Absorption and Fluorescence Line-Narrowing Measurements

Cited by 176 publications

References 23 publications

Laser-Limited Signatures of Quantum Coherence

Laser-Limited Signatures of Quantum Coherence

Exploiting Structured Environments for Efficient Energy Transfer: The Phonon Antenna Mechanism

Vibration-assisted resonance in photosynthetic excitation-energy transfer

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