Quantum Coherence Enabled Determination of the Energy Landscape in Light-Harvesting Complex II

Calhoun, Tessa R.; Ginsberg, Naomi S.; Schlau‐Cohen, Gabriela S.; Cheng, Yuan‐Chung; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R.

doi:10.1021/jp908300c

Cited by 280 publications

(313 citation statements)

References 27 publications

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“…In the first case, the evolution operator U (eeee) (T ) appearing in Eqs. (29) and (30) is calculated by standard time dependent CL-QME derived using AK projector, Eq. (22).…”

Section: Numerical Results and Discussionmentioning

confidence: 99%

Parametric projection operator technique for second order non-linear response

Olšina¹,

Mančal²

2012

Chemical Physics

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We demonstrate the application of the recently introduced parametric projector operator technique to a calculation of the second order non-linear optical response of a multilevel molecular system. We derive a parametric quantum master equation (QME) for the time evolution of the excited state of an excitonic system after excitation by the first two pulses in the usual spectroscopic four-wave-mixing scheme. This master equation differs from the usual QME by a correction term which depends on the delay τ between the pulses. In the presence of environmental degrees of freedom with finite bath correlation time and in the presence of intramolecular vibrations we find distinct dynamics of both the excite state populations and the electronic coherence for different delays τ .

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“…In the first case, the evolution operator U (eeee) (T ) appearing in Eqs. (29) and (30) is calculated by standard time dependent CL-QME derived using AK projector, Eq. (22).…”

Section: Numerical Results and Discussionmentioning

confidence: 99%

Parametric projection operator technique for second order non-linear response

Olšina¹,

Mančal²

2012

Chemical Physics

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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%

“…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. 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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“…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].…”

mentioning

confidence: 99%

“…Coherent inter-site couplings in H S can be stronger or of the same order than the characteristic strength of the environmental interactions [1,3,4,23]. In such cases delocalised exciton eigenstates, for which H S is diagonal, therefore provide the preferred basis to analyze the system's transport dynamics.…”

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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Quantum Coherence Enabled Determination of the Energy Landscape in Light-Harvesting Complex II

Cited by 280 publications

References 27 publications

Parametric projection operator technique for second order non-linear response

Parametric projection operator technique for second order non-linear response

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

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

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