Effects of finite laser pulse width on two-dimensional electronic spectroscopy

Leng, Xuan; Yue, Shuai; Weng, Yuxiang; Song, Kai; Shi, Qiang

doi:10.1016/j.cplett.2016.11.030

Cited by 21 publications

(32 citation statements)

References 49 publications

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“…Leng et al 89 then extended this work by using the HEOM to simulate the quantum dynamics beyond the perturbatively GQMEs originally used in Reference 92. For simplicity, detailed expressions for such calculations are not given here, and can be referred to these previous works 85,89,92 . By using this approach, it was found that finite pulse effects can have significant influences on the measured 2DES signals, 89 by distorting both the 2DES peak shapes and the evolution of diagonal and off‐diagonal peaks.…”

Section: Theorymentioning

confidence: 99%

“…Another approach to simulate the nonlinear spectroscopic signals is based on direct calculation of the molecular polarizabilities with an explicit external field, [84][85][86][87][88][89] This approach was originally proposed by Domcke and coworkers in References 84 and 90. In this method, quantum dynamics of the molecular system is simulated by applying the electromagnetic field explicitly, and specific spectroscopic signals are obtained by combing results using predefined sets of pulse sequences with different phase factors.…”

Section: Direct Calculation Of Molecular Responsesmentioning

confidence: 99%

“…An important advantage of the direct simulation method (also called the phase-matching approach in the literature) is that it is not limited to the assumption of weak laser fields, and it allows efficient simulation of the nonlinear spectroscopic signals with arbitrary pulse durations and pulse overlap effects. Although in practical calculations, 89,92 the RWA and the weak-field approximation are often used to reduce the computational costs, the extension to the strong field case is straightforward by including more phase-matching terms. 85,93 Therefore, the direct simulation method can be applied to study more complex interactions between the laser field and the photosynthetic light-harvesting complexes.…”

Section: Direct Calculation Of Molecular Responsesmentioning

confidence: 99%

“…By using the direct simulation method presented in Section 2.3.2, such effects were investigated for a model dimer. 89 It was shown that the two diagonal peaks shift towards to the center frequency of the laser pulses as the pulse bandwidth became narrower. When the laser pulse durations become longer, besides the reduced peak widths due to the finite bandwidth effect, the peaks are also rotated compared to the impulsive limit.…”

Section: Absorption Emissionmentioning

confidence: 99%

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Theoretical study of excitation energy transfer and nonlinear spectroscopy of photosynthetic light‐harvesting complexes using the nonperturbative reduced dynamics method

Yan

Xing

et al. 2020

WIREs Comput Mol Sci

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The highly efficient excitation energy transfer (EET) processes in photosynthetic light‐harvesting complexes have attracted much recent research interests. Experimentally, spectroscopic studies have provided important information on the energetics and EET dynamics. Theoretically, due to the large number of degrees of freedom and the complex interaction between the pigments and the protein environment, it is impossible to simulate the whole system quantum mechanically. Effective Hamiltonian models are often used, in which the most important degrees of freedom are treated explicitly and all the other degrees of freedom are treated as a thermal bath. However, even with such simplifications, solving the real‐time quantum dynamics could still be a difficult task. A particular challenging case in simulating the EET dynamics and related spectroscopic phenomena lies in the so‐called intermediate coupling regime, where the intermolecular electronic couplings and the electronic–vibrational couplings are of similar strength. In this article, we review theoretical studies of linear and nonlinear spectroscopic signals of photosynthetic light‐harvesting complexes, using the nonperturbative hierarchical equations of motion (HEOM) approach. Simulations were performed for the EET dynamics, various types of linear spectra, two‐dimensional electronic spectra, and pump–probe spectra. Benchmark tests of several approximate methods related to the HEOM approach were also discussed. The results show that the nonperturbative HEOM approach is an effective method in simulating the EET dynamics and spectroscopic signals of photosynthetic light‐harvesting complexes. Important insights into EET pathways, quantum effects including quantum delocalization, and quantum coherence in photosynthetic light‐harvesting complexes were also obtained through such simulations. This article is categorized under: Theoretical and Physical Chemistry > Reaction Dynamics and Kinetics Theoretical and Physical Chemistry > Spectroscopy Software > Simulation Methods

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Section: Theorymentioning

confidence: 99%

Section: Direct Calculation Of Molecular Responsesmentioning

confidence: 99%

Section: Direct Calculation Of Molecular Responsesmentioning

confidence: 99%

Section: Absorption Emissionmentioning

confidence: 99%

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Theoretical study of excitation energy transfer and nonlinear spectroscopy of photosynthetic light‐harvesting complexes using the nonperturbative reduced dynamics method

Yan

Xing

et al. 2020

WIREs Comput Mol Sci

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“…To calculate N for each damping strength, we compare the dynamics of the system with and without excitation due to a Gaussian laser pulse. Adopting the semiclassical approximation for a real laser field, the systemfield interaction Hamiltonian is given by, 42,43…”

Section: Theoretical Modelmentioning

confidence: 99%

Quantifying non-Markovianity in underdamped versus overdamped environments and its effect on spectral lineshape

Green

Humphries

Dijkstra

et al. 2019

The Journal of Chemical Physics

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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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Effects of finite laser pulse width on two-dimensional electronic spectroscopy

Cited by 21 publications

References 49 publications

Theoretical study of excitation energy transfer and nonlinear spectroscopy of photosynthetic light‐harvesting complexes using the nonperturbative reduced dynamics method

Theoretical study of excitation energy transfer and nonlinear spectroscopy of photosynthetic light‐harvesting complexes using the nonperturbative reduced dynamics method

Quantifying non-Markovianity in underdamped versus overdamped environments and its effect on spectral lineshape

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

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