Equation-of-Motion Methods for the Calculation of Femtosecond Time-Resolved 4-Wave-Mixing and <i>N</i>-Wave-Mixing Signals

Gelin, Maxim F.; Chen, Lipeng; Domcke, Wolfgang

doi:10.1021/acs.chemrev.2c00329

Cited by 30 publications

(20 citation statements)

References 719 publications

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“…However, established quantum dynamics methods can struggle with the combination of strong electronvibrational coupling and spatially-extended structures characteristic of molecular aggregates. 6 As a result, the development of efficient algorithms for simulating time-resolved optical spectroscopy measurements of extended molecular aggregates remains a persistent challenge.…”

Section: Introductionmentioning

confidence: 99%

Simulating optical linear absorption for mesoscale molecular aggregates: an adaptive hierarchy of pure states approach

Gera¹,

Chen²,

Eisfeld³

et al. 2023

Preprint

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In this paper, we present a new method for calculating linear absorption spectra for large molecular aggregates, called dyadic adaptive HOPS (DadHOPS). This method combines the adaptive HOPS (adHOPS) framework, which uses locality to improve computational scaling, with the dyadic HOPS method previously developed to calculate linear and non-linear spectroscopic signals. To construct a local representation of dyadic HOPS, we introduce an initial state decomposition which reconstructs the linear absorption spectra from a sum over locally excited initial conditions. We demonstrate the sum over initial conditions can be efficiently Monte Carlo sampled, that the corresponding calculations achieve size-invariant (i.e. O(1)) scaling for sufficiently large aggregates, and that it allows for the trivial inclusion of static disorder in the Hamiltonian. We present calculations on the photosystem I core complex to explore the behavior of the initial state decomposition in complex molecular aggregates, and proof-of-concept DadHOPS calculations on an artificial molecular aggregate inspired by perylene bis-imide.

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Section: Introductionmentioning

confidence: 99%

Simulating optical linear absorption for mesoscale molecular aggregates: an adaptive hierarchy of pure states approach

Gera¹,

Chen²,

Eisfeld³

et al. 2023

Preprint

View full text Add to dashboard Cite

show abstract

“…By selecting an appropriate model and controlling the relevant parameters, theoretical simulations can identify the origin of the signals in 2DES and thus provide explanations for the experimental observations. 7,40 In this work, we simulate the all-parallel (AP) and DC-2DRS of a minimalist model, in which only the electronic transition of the lower-energy chromophore is coupled to a vibrational mode, by using the numerically exact hierarchical equations of motion method. 41,42 Combining the DC-2DRS and 2DBMs, we differentiate the various types of coherence in 2DRS on the basis of the fact that the population and vibrational coherence signals are largely suppressed.…”

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confidence: 99%

“…The orientational disorders are implemented by a linear combination of molecular frame responses as shown in eq S9. 40 To compare the two sets of spectra, each spectrum is normalized by the maximal magnitude occurring at T = 0 fs of each set of spectra. The lower diagonal-peak (DP) position is also shifted to (0, 0).…”

mentioning

confidence: 99%

“…However, the experimental results are often interwoven with multiple signals due to the interaction between various chromophores and vibrational modes, which makes it challenging to analyze the observed 2D spectra. By selecting an appropriate model and controlling the relevant parameters, theoretical simulations can identify the origin of the signals in 2DES and thus provide explanations for the experimental observations. , In this work, we simulate the all-parallel (AP) and DC-2DRS of a minimalist model, in which only the electronic transition of the lower-energy chromophore is coupled to a vibrational mode, by using the numerically exact hierarchical equations of motion method. , Combining the DC-2DRS and 2DBMs, we differentiate the various types of coherence in 2DRS on the basis of the fact that the population and vibrational coherence signals are largely suppressed. The results could serve as a paradigm template to assist in understanding the coherence types in polarization-dependent 2DRS observed in the experiment.…”

mentioning

confidence: 99%

“…For comparison, results with static disorder are presented in Figures S5–S7. The orientational disorders are implemented by a linear combination of molecular frame responses as shown in eq S9 . To compare the two sets of spectra, each spectrum is normalized by the maximal magnitude occurring at T = 0 fs of each set of spectra.…”

mentioning

confidence: 99%

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Revealing Intermolecular Electronic and Vibronic Coherence with Polarization-Dependent Two-Dimensional Beating Maps

Leng

Yan

Zhu

et al. 2023

J. Phys. Chem. Lett.

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Two-dimensional electronic spectroscopy (2DES) has been widely employed as an efficient tool to reveal the impact of intermolecular electronic and/ or vibronic quantum coherence on excitation energy transfer in light-harvesting complexes. However, intramolecular vibrational coherence would also contribute to oscillating signals in 2D spectra, along with the intermolecular coherence signals that are directly related to energy transfer. In this work, the possibility of screening the vibrational coherence signals is explored through polarization-dependent 2DES. The all-parallel (AP) and double-crossed (DC) polarization-dependent two-dimensional rephasing spectra (2DRS) are simulated for a minimalist heterodimer model with vibrational coupling. By combining the DC-2DRS and the 2D beating maps, we demonstrate that the population and vibrational coherence signals can be largely suppressed, resulting in highlighted intermolecular electronic and vibronic coherence signals. Moreover, the AP-and DC-2DBMs show rather different patterns at the vibrational frequency, indicating a possible way to identify pure vibrational coherence.

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Advanced quantum and semiclassical methods for simulating photoinduced molecular dynamics and spectroscopy

Faraji,

Picconi,

Palacino‐González

2024

WIREs Comput Mol Sci

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Molecular‐level understanding of photoinduced processes is critically important for breakthroughs in transformative technologies utilizing light, ranging from photomedicine to photoresponsive materials. Theory and simulation play a crucial role in this task. Despite great advances in hardware and computational methods, the theoretical description of photoinduced phenomena in the presence of complex environments and external photoexcitation conditions still poses formidable challenges for theoreticians and there are numerous formal and computational difficulties that must be overcome. The development of predictive, accurate, and at the same time, computationally efficient theoretical approaches to describe complex problems in photochemistry and photophysics is an active field of research in contemporary theoretical and computational chemistry. In this advanced review, we discuss modern computational advances and novel approaches that have been recently developed in excited‐electronic structure methods, and multiscale modeling, with a special emphasis on coupled electron‐nuclear dynamics and spectroscopy, from fully quantum to semi‐classical methodologies—including dissipative effects, the explicit light field interaction, femtosecond time‐resolved spectroscopy, and software infrastructure.This article is categorized under: Software > Quantum Chemistry Electronic Structure Theory > Combined QM/MM Methods Theoretical and Physical Chemistry > Spectroscopy Software > Molecular Modeling

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Equation-of-Motion Methods for the Calculation of Femtosecond Time-Resolved 4-Wave-Mixing and N-Wave-Mixing Signals

Cited by 30 publications

References 719 publications

Simulating optical linear absorption for mesoscale molecular aggregates: an adaptive hierarchy of pure states approach

Simulating optical linear absorption for mesoscale molecular aggregates: an adaptive hierarchy of pure states approach

Revealing Intermolecular Electronic and Vibronic Coherence with Polarization-Dependent Two-Dimensional Beating Maps

Advanced quantum and semiclassical methods for simulating photoinduced molecular dynamics and spectroscopy

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