Simulation of the two-dimensional electronic spectra of the Fenna-Matthews-Olson complex using the hierarchical equations of motion method

Chen, Liping; Zheng, Ren-Hui; Jing, Yuanyuan; Shi, Qiang

doi:10.1063/1.3589982

Cited by 117 publications

(152 citation statements)

References 67 publications

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“…Fig. 5 shows a close up of spectral densities discussed in the main text, and in additions includes for convenient reference the single-peak Drude-Lorentz density (dotted line, J DL ), used in some previous studies [17][18][19]. …”

Section: Appendixmentioning

confidence: 99%

“…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 oscillations are absent already at T = 77 K [19]. Hence the search continues for theoretical models which support a long-lasting coherent dynamics leading to cross-peak oscillations in 2d echo-spectra and simultaneously retain the fast dissipation.…”

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confidence: 99%

“…1) has been extracted from fluorescence-linenarrowing experiments at T = 4 K [31,32] and shows a super-Ohmic behaviour. However, previous calculations of 2d-echo spectra of seven-site FMO complex have been often performed with a single-peak Drude-Lorentz spectral density [18,19], and did not yield long-lasting cross-peak oscillations. The situation is different in the population dynamics, which has been analyzed for different spectral densities [26] and yields no significant differences in the duration of population beatings for different spectral density.…”

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confidence: 99%

“…The computation of the 2d echo-signal for the FMO complex necessitates about 10 3 more time-steps than the calculation of the population dynamics and has only recently been achieved for the non-Markovian case [18,19]. We solve the exciton dynamics within the hierarchical equation of motion (HEOM) formalism [24,25].…”

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confidence: 99%

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

Kreisbeck

Kramer

2012

J. Phys. Chem. Lett.

236

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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Section: Appendixmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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

Kreisbeck

Kramer

2012

J. Phys. Chem. Lett.

236

320

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“…By generalizing hierarchy structures, one can deal with a low temperature system 45,59,60 as well as general spectral distributions 61 including Brownian spectral distributions [62][63][64][65] and a Lorentzian distribution. 66,67 This formalism is valuable since it can handle not only strong system-bath coupling, but also quantum coherence between the system and bath, which plays important roles in multidimensional spectroscopy, [50][51][52][53][54][55][67][68][69] energy transfer processes in photosynthetic antenna systems [70][71][72][73][74][75][76][77] and DNA systems, 78 ET process, 49,79 and processes discussed in a quantum information theory. [80][81][82][83] While most research with the HEOM approach assumed the Drude spectral distribution, we have shown that the ET problem can be handled in a nonperturbative manner for both the system-bath and ET couplings by applying the hierarchy formalism to the Brownian oscillator (BO) spectral distribution that arises from the canonical transformation of ET system.…”

Section: Introductionmentioning

confidence: 99%

Reduced hierarchy equations of motion approach with Drude plus Brownian spectral distribution: Probing electron transfer processes by means of two-dimensional correlation spectroscopy

Tanimura

2012

The Journal of Chemical Physics

129

137

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Quantum heat current under non-perturbative and non-Markovian conditions: Applications to heat machinesWe theoretically investigate an electron transfer (ET) process in a dissipative environment by means of two-dimensional (2D) correlation spectroscopy. We extend the reduced hierarchy equations of motion approach to include both overdamped Drude and underdamped Brownian modes. While the overdamped mode describes the inhomogeneity of a system in the slow modulation limit, the underdamped mode expresses the primary vibrational mode coupled with the electronic states. We outline a procedure for calculating 2D correlation spectrum that incorporates the ET processes. The present approach has the capability of dealing with system-bath coherence under an external perturbation, which is important to calculate nonlinear response functions for non-Markovian noise. The calculated 2D spectrum exhibits the effects of the ET processes through the presence of ET transition peaks along the 1 axis, as well as the decay of echo signals.

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Two‐dimensional electronic spectrum simulation of simple photosynthetic complex models with semi‐classical Poisson bracket mapping equation

Kim

Rhee

2022

Bulletin Korean Chem Soc

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As understanding experimentally observed two-dimensional electronic spectroscopy (2DES) signals usually requires theoretical modeling, various approaches have been applied to simulating the spectra. It will be desirable to develop a method that is free from parameters that are adjusted based on spectroscopic outcomes. Often, such parameters without any a priori known information come from quantum chemical calculations that can only be achieved at the atomistic resolution, and a necessity arises for designing a scheme that can be readily used for generating 2DES spectra even for atomistic models of complex systems. Here, we present such an approach based on mixed quantum-classical Poisson bracket mapping equation formalism, which can be extended to all-atom simulations. We check its performance by adopting a two-state toy model and show that we can efficiently construct 2D spectra. We show that our scheme can yield reasonable 2D spectra even when high-frequency vibrations modulate the population dynamics.

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Simulation of the two-dimensional electronic spectra of the Fenna-Matthews-Olson complex using the hierarchical equations of motion method

Cited by 117 publications

References 67 publications

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

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

Reduced hierarchy equations of motion approach with Drude plus Brownian spectral distribution: Probing electron transfer processes by means of two-dimensional correlation spectroscopy

Two‐dimensional electronic spectrum simulation of simple photosynthetic complex models with semi‐classical Poisson bracket mapping equation

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