Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature

Collini, Elisabetta; Wong, C.; Wilk, Krystyna E.; Curmi, Paul M. G.; Brumer, Paul; Scholes, Gregory D.

doi:10.1038/nature08811

Cited by 1,530 publications

(1,797 citation statements)

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“…This idea found further support in a subsequent series of measurements that showed spectral beatings for cryptophyte algae [3] and Photosystem II protein complexes [9], indicating that coherent behavior in biological systems is ubiquitous. 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].…”

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%

“…Recent advances in ultrafast nonlinear spectroscopy have revived the discussion on the role of quantum dynamics in biological photosynthesis [1][2][3]. The extension of two-dimensional (2D) spectroscopy to the visible range [4] has allowed light-harvesting complexes to be investigated in great detail [5,6], revealing electronic energy transfer between the coupled pigments [5,7].…”

Section: Introductionmentioning

confidence: 99%

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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: 99%

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Laser-Limited Signatures of Quantum Coherence

et al. 2015

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“…6,10 Another new class of applications of classical MD is the elucidation of experiments in ultrafast electronic spectroscopy of biomolecules. It was recently shown that long quantum coherences can be observed in biological molecules [11][12][13] and the aim of atomistic simulations is to explain how the (classical) environment can influence the (quantum) evolution of the electronic states. [14][15][16][17][18] Also for the applications in photobiology, MD simulations are often coupled with electronic structure methods to describe aspects of the quantum dynamics.…”

Section: Introductionmentioning

confidence: 99%

Developing accurate molecular mechanics force fields for conjugated molecular systems

Troisi

2015

Phys. Chem. Chem. Phys.

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A rapid method to parameterize the intramolecular component of classical force fields for complex conjugated molecules is proposed. The method is based on a procedure of force matching with a reference electronic structure calculation. It is particularly suitable for those applications where molecular dynamics simulations are used to generate structures that are therefore analysed with electronic structure methods, because it is possible to build force fields that are consistent with the electronic structure calculations that follow the classical simulations. Such applications are commonly encountered in organic electronics, spectroscopy of complex systems and photobiology (e.g. photosynthetic systems). We illustrate the method by parameterizing the force fields of a molecule used in molecular semiconductors (2,2-dicyanovinyl-capped S, N-heteropentacene or DCV-SN5), a polymeric semiconductor (thieno[3,2-b]thiophene-diketopyrrolopyrrole TT-DPP) and a chromophore embedded in a protein environment (15,16-Dihydrobiliverdin or DBV) where several hundreds of parameters need to be optimized in parallel.

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“…Yz, 78.47.nj, 05.60.Gg Long-lasting oscillatory signals in optically excited light-harvesting complexes (LHCs) point towards the prevalence of a coherent electronic dynamics in molecular networks at physiological temperatures [2][3][4][5]. The experiments probe the electronic dynamics using twodimensional (2d) echo-spectroscopy for a series of delaytimes between the excitation pulse and the probe pulse.…”

mentioning

confidence: 99%

Long-Lived Electronic Coherence in Dissipative Exciton Dynamics of Light-Harvesting Complexes

Kreisbeck

Kramer

2012

J. Phys. Chem. Lett.

233

320

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The observed prevalence of oscillatory signals in the spectroscopy of biological light-harvesting complexes at ambient temperatures has led to a search for mechanisms supporting coherent transport through larger molecules in noisy environments. We demonstrate a generic mechanism supporting long-lasting electronic coherence up to 0.3 ps at a temperature of 277 K. The mechanism relies on two properties of the spectral density: (i) a large dissipative coupling to a continuum of higherfrequency vibrations required for efficient transport and (ii) a small slope of the spectral density at zero frequency.PACS numbers: 03.65. Yz, 78.47.nj, 05.60.Gg Long-lasting oscillatory signals in optically excited light-harvesting complexes (LHCs) point towards the prevalence of a coherent electronic dynamics in molecular networks at physiological temperatures [2][3][4][5]. The experiments probe the electronic dynamics using twodimensional (2d) echo-spectroscopy for a series of delaytimes between the excitation pulse and the probe pulse. The 2d spectroscopy makes studies of the dynamics of dissipative systems possible and has found further applications in mesoscopic systems such as molecular nanotubes [6] and semiconductor devices [7]. Due to its known crystallographic structure and relative simplicity, the Fenna-Matthews-Olson (FMO) complex serves as the prototype system for studying the choreography of the energy transfer from the antenna to the reaction center of a light harvesting complex [8]. In 2d spectra long-lasting beatings are observed, ranging from 1.2 ps at T = 150 K to 0.3 ps at T = 277 K [9]. The interplay of coherent dynamics, which leads to a delocalization of an initial excitation arriving at the FMO network from the antenna, and the coupling to a vibronic environment with slow and fast fluctuations, has lead to studies of environmentally assisted transport in LHCs [10,11].An important open question is whether coherence plays a key-role in the functioning of light-harvesting complexes [8]. The theoretical understanding of the experiments is in its early stages and atomistic simulations based on molecular dynamics have not reached agreement [12,13]. A calculation of 2d echo-spectra based on the molecular dynamics simulation [14] does not show clear coherent oscillations at T = 277 K. One key ingredient for efficient transfer dynamics is the strong coupling to vibronic modes, which induces energy dissipation [10,11,15]. For the FMO complex the thermalization occurs within picoseconds and was observed by Brixner et al. by the decay of diagonal-peak amplitudes to lower energies [16]. It has been proposed that the inclusion of the finite time scale of the reorganization process gives rise to long-lasting coherence in LHCs [17]. While a sluggish bath relaxation leads to prolonged population beatings in the FMO network, calculations of 2d echo-spectra show oscillations of the exciton cross-peaks for only about 1/6th of the experimentally recorded time at T = 150 K [18]. For an even longer bath-relaxation cross-peak osci...

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Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature

Cited by 1,530 publications

References 30 publications

Laser-Limited Signatures of Quantum Coherence

Laser-Limited Signatures of Quantum Coherence

Developing accurate molecular mechanics force fields for conjugated molecular systems

Long-Lived Electronic Coherence in Dissipative Exciton Dynamics of Light-Harvesting Complexes

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