How the molecular structure determines the flow of excitation energy in plant light-harvesting complex II

Renger, Thomas; Madjet, Mohamed; Knorr, Andreas; Müh, Frank

doi:10.1016/j.jplph.2011.01.004

Cited by 84 publications

(185 citation statements)

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“…57 The time-scale for the Chlb/Chla transfer obtained by both methods differs by one order of magnitude. 27,32,[34][35][36][37] The combined Förster-Redfield theory requires an empirical parameter M cr for separating the exciton Hamiltonian between a strongly coupled part H strong ex with all off-diagonal elements set to zero except those |J mn | > M cr and the remaining weakly coupled sites. 58 Suggested values for LHC II are M cr = 20 cm −1 or smaller.…”

Section: Influence Of the Vibrational Peaks On The Transport In Lhc IImentioning

confidence: 99%

“…16,30,31 However, 2d echo-spectra are more susceptible to vibrational modes and reflect both, electronic and vibrational effects. 10 Due to the lack of computational capabilities, energy-transfer in LHC II had been previously calculated only with approximate methods [32][33][34] with non-conclusive results for the transfer timescales. The predictions for the relaxation time differ by more than one order of magnitude 27,32,[35][36][37] from the results of Renger et al 34 Approximate methods work best in specific limits of delocalized (Redfield type) or incoherent dynamics (Förster transfer), or alternatively try to interpolate between the two cases.…”

Section: Introductionmentioning

confidence: 99%

“…10 Due to the lack of computational capabilities, energy-transfer in LHC II had been previously calculated only with approximate methods [32][33][34] with non-conclusive results for the transfer timescales. The predictions for the relaxation time differ by more than one order of magnitude 27,32,[35][36][37] from the results of Renger et al 34 Approximate methods work best in specific limits of delocalized (Redfield type) or incoherent dynamics (Förster transfer), or alternatively try to interpolate between the two cases. Any interpolation and combination of Förster/Redfield methods requires to introduce an empirical cut-off parameter, which depends on the precise system parameters (excitonic energies) as well as on the environment (temperature).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Scalable High-Performance Algorithm for the Simulation of Exciton Dynamics. Application to the Light-Harvesting Complex II in the Presence of Resonant Vibrational Modes

Kreisbeck

Kramer

Aspuru‐Guzik

2014

J. Chem. Theory Comput.

118

160

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The accurate simulation of excitonic energy transfer in molecular complexes with coupled electronic and vibrational degrees of freedom is essential for comparing excitonic systemparameters obtained from ab-initio methods with measured time-resolved spectra. Several exact methods for computing the exciton dynamics within a density-matrix formalism are known, * To whom correspondence should be addressed † Institut für Physik, Humboldt-Universität zu Berlin, Newtonstr. 15, 12489 Berlin, Germany ‡ Mads Clausen Institute, University of Southern Denmark, Alsion 2, 6400 Sønderborg, Denmark ¶ Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St, Cambridge, Massachusetts 02138, USA 1 but are restricted to small systems with less than ten sites due to their computational complexity. To study the excitonic energy transfer in larger systems, we adapt and extend the exact hierarchical equation of motion (HEOM) method to various high-performance many-core platforms using the Open Compute Language (OpenCL). For the light-harvesting complex II (LHC II) found in spinach, the HEOM results deviate from predictions of approximate theories and clarify the time-scale of the transfer-process. We investigate the impact of resonantly coupled vibrations on the relaxation and show that the transfer does not rely on a fine-tuning of specific modes.

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Section: Influence Of the Vibrational Peaks On The Transport In Lhc IImentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Scalable High-Performance Algorithm for the Simulation of Exciton Dynamics. Application to the Light-Harvesting Complex II in the Presence of Resonant Vibrational Modes

Kreisbeck

Kramer

Aspuru‐Guzik

2014

J. Chem. Theory Comput.

118

160

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“…Previously, the "bottleneck" state was assumed to be on Chl 604, 5,35 but calculations by Renger et al 8 predict, on one hand, red-shifted Chl 604 and, on the other hand, slow energy transfer (tens of ps) from Chl 613/614. It remains a possibility, albeit unlikely, that in aggregates, fast energy transfer (∼3 ps time scale) occurs from the peripherally positioned Chl 613/614 pair to Chls on the nearest neighbour complex.…”

Section: On the Identity Of The Intermediate Statesmentioning

confidence: 99%

“…2,3 In addition, modelling the excitonic couplings and site energies of the 14 chlorophylls (Chls) based on the crystal structure 2,4 has been used to predict the downhill Chl energy transfer routes and ultrafast dynamics. [5][6][7][8][9] In addition to the light-harvesting function, LHCII is involved in the non-radiative dissipation of excess excitation energy, a process collectively referred to as non-photochemical quenching (NPQ) of Chl fluorescence, [10][11][12] a key mechanism for protection against photodamage under excess radiation levels. In vitro, significant quenching manifested in shortening a) Electronic mail: lambrev@brc.hu b) Electronic mail: howesiang@ntu.edu.sg of the Chl a excitation lifetime [13][14][15][16] and development of a farred emitting state 17,18 are observed upon protein aggregation of LHCII.…”

Section: Introductionmentioning

confidence: 99%

Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy

Enriquez

Akhtar

Zhang

et al. 2015

The Journal of Chemical Physics

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The pathways and dynamics of excitation energy transfer between the chlorophyll (Chl) domains in solubilized trimeric and aggregated light-harvesting complex II (LHCII) are examined using two-dimensional electronic spectroscopy (2DES). The LHCII trimers and aggregates exhibit the unquenched and quenched excitonic states of Chl a, respectively. 2DES allows direct correlation of excitation and emission energies of coupled states over population time delays, hence enabling mapping of the energy flow between Chls. By the excitation of the entire Chl b Q y band, energy transfer from Chl b to Chl a states is monitored in the LHCII trimers and aggregates. Global analysis of the two-dimensional (2D) spectra reveals that energy transfer from Chl b to Chl a occurs on fast and slow time scales of 240-270 fs and 2.8 ps for both forms of LHCII. 2D decay-associated spectra resulting from the global analysis identify the correlation between Chl states involved in the energy transfer and decay at a given lifetime. The contribution of singlet-singlet annihilation on the kinetics of Chl energy transfer and decay is also modelled and discussed. The results show a marked change in the energy transfer kinetics in the time range of a few picoseconds. Owing to slow energy equilibration processes, long-lived intermediate Chl a states are present in solubilized trimers, while in aggregates, the population decay of these excited states is significantly accelerated, suggesting that, overall, the energy transfer within the LHCII complexes is faster in the aggregated state. C 2015 AIP Publishing LLC. [http://dx

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Hierarchical Equations of Motion Simulation of Temperature‐Dependent Two‐Dimensional Electronic Spectroscopy of the Chlorophyll a Manifold in LHCII

Leng

Nhut

Akhtar

et al. 2020

Chemistry An Asian Journal

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We simulated two‐dimensional electronic spectra (2DES) of the chlorophyll a manifold of light‐harvesting complex II (LHCII) at various temperatures (77, 110, 150, 190, 230, 273, and 293 K) using the hierarchical equations of the motion‐phase matching approach. We confirm the main excitation energy transfer pathways assignments within the chlorophyll a manifold of LHCII measured in a recent work (J. Phys. Chem. B 2019, 123, 6765–6775). The calculated transfer rates are also in general agreement with the measured rates. We also provided theoretical confirmation for the experimental assignments, as uphill and downhill energy transfer processes, of 2D spectral features that were reported in recent experimental reports. These temperature‐dependent features were also ascertained to follow the detailed‐balance principle.

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How the molecular structure determines the flow of excitation energy in plant light-harvesting complex II

Cited by 84 publications

References 50 publications

Scalable High-Performance Algorithm for the Simulation of Exciton Dynamics. Application to the Light-Harvesting Complex II in the Presence of Resonant Vibrational Modes

Scalable High-Performance Algorithm for the Simulation of Exciton Dynamics. Application to the Light-Harvesting Complex II in the Presence of Resonant Vibrational Modes

Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy

Hierarchical Equations of Motion Simulation of Temperature‐Dependent Two‐Dimensional Electronic Spectroscopy of the Chlorophyll a Manifold in LHCII

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