Formally exact simulations of mesoscale exciton dynamics in molecular materials

Varvelo, Leonel; Lynd, Jacob K.; Bennett, Doran I. G.

doi:10.1039/d1sc01448j

Cited by 30 publications

(31 citation statements)

References 82 publications

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“…It should be noted that the new formalism developed here needs many fewer stochastic trajectories to obtain converged 2D spectra when compared to those calculated by a non-perturbative phase-cycling scheme. 31 As compared to density matrix based methods, the non-linear NMQSD method propagates vectors instead of matrices, individual simulations with different noise trajectories are trivially parallel and, furthermore, it is consistent with adaptive basis 29 and tensor contraction 30 approaches recently developed for HOPS. Our theory thus offers a promising technique to simulate 2D spectra of large molecular aggregates.…”

Section: Discussionmentioning

confidence: 69%

“…36. It is also possible to use an adaptive algorithm to reduce the size of the hierarchy 29 or use a matrix product state representation. 30…”

Section: E Hops For Solving the Nmqsd Propagationmentioning

confidence: 99%

“…An alternative to density matrix based methods is the non-Markovian quantum state diffusion (NMQSD) formalism, in which stochastic wavefunctions are propagated in the system Hilbert space and the density matrix is obtained from an average of these wavefunctions. 24,25 Over the years, sev-eral approaches have been developed to efficiently solve the NMQSD equation numerically, [26][27][28][29][30] so that simulations of excitation transport in large molecular aggregates containing thousands of pigments are now tractable. In these propagation schemes, importance sampling via the non-linear NMQSD equations are essential for efficient convergence with respect to the number of trajectories.…”

Section: Introductionmentioning

confidence: 99%

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Calculating non-linear response functions for multi-dimensional electronic spectroscopy using dyadic non-Markovian quantum state diffusion

Chen,

Bennett,

Eisfeld

2022

Preprint

Self Cite

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Section: Discussionmentioning

confidence: 69%

“…36. It is also possible to use an adaptive algorithm to reduce the size of the hierarchy 29 or use a matrix product state representation. 30…”

Section: E Hops For Solving the Nmqsd Propagationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Calculating non-linear response functions for multi-dimensional electronic spectroscopy using dyadic non-Markovian quantum state diffusion

Chen,

Bennett,

Eisfeld

2022

Preprint

Self Cite

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“…However, an extension of the multiscale approach to make the spectroscopic calculation span multiple lengths and/or time scales is a new challenge. A few promising steps in this direction include the development of efficient methods for predicting the dynamics of excited states in extensive systems such as the kinetic network model, [265][266][267] DM-HEOM, 219 and multi-chromophoric Förster energy transfer models. 76,268 Combining such approaches to calculate time-resolved spectra for large complex systems will be an important new direction.…”

Section: Concluding Discussion and Future Directionsmentioning

confidence: 99%

Computational spectroscopy of complex systems

Jansen

2021

The Journal of Chemical Physics

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Numerous linear and non-linear spectroscopic techniques have been developed to elucidate structural and functional information of complex systems ranging from natural systems, such as proteins and light-harvesting systems, to synthetic systems, such as solar cell materials and light-emitting diodes. The obtained experimental data can be challenging to interpret due to the complexity and potential overlapping spectral signatures. Therefore, computational spectroscopy plays a crucial role in the interpretation and understanding of spectral observables of complex systems. Computational modeling of various spectroscopic techniques has seen significant developments in the past decade, when it comes to the systems that can be addressed, the size and complexity of the sample types, the accuracy of the methods, and the spectroscopic techniques that can be addressed. In this Perspective, I will review the computational spectroscopy methods that have been developed and applied for infrared and visible spectroscopies in the condensed phase. I will discuss some of the questions that this has allowed answering. Finally, I will discuss current and future challenges and how these may be addressed.

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“…An accurate account of exciton dynamics in light harvesting systems goes beyond perturbative and Markovian approximations [1]. Much progress on non-perturbative and non-Markovian treatments has been achieved over past few years [21,22], such as the hierarchy equation of motion (HEOM) [23,24], the multilayer multiconfiguration time-dependent Hartree methods [22], and the hierarchy of pure states equations [25,26]. In order to circumvent numerical difficulties encountered by many nonperturbative approaches, the Dirac-Frenkel time-dependent variational principle has been adopted to investigate the real time exciton-phonon dynamics [27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

Fully Quantum Modeling of Exciton Diffusion in Mesoscale Light Harvesting Systems

et al. 2021

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It has long been a challenge to accurately and efficiently simulate exciton–phonon dynamics in mesoscale photosynthetic systems with a fully quantum mechanical treatment due to extensive computational resources required. In this work, we tackle this seemingly intractable problem by combining the Dirac–Frenkel time-dependent variational method with Davydov trial states and implementing the algorithm in graphic processing units. The phonons are treated on the same footing as the exciton. Tested with toy models, which are nanoarrays of the B850 pigments from the light harvesting 2 complexes of purple bacteria, the methodology is adopted to describe exciton diffusion in huge systems containing more than 1600 molecules. The superradiance enhancement factor extracted from the simulations indicates an exciton delocalization over two to three pigments, in agreement with measurements of fluorescence quantum yield and lifetime in B850 systems. With fractal analysis of the exciton dynamics, it is found that exciton transfer in B850 nanoarrays exhibits a superdiffusion component for about 500 fs. Treating the B850 ring as an aggregate and modeling the inter-ring exciton transfer as incoherent hopping, we also apply the method of classical master equations to estimate exciton diffusion properties in one-dimensional (1D) and two-dimensional (2D) B850 nanoarrays using derived analytical expressions of time-dependent excitation probabilities. For both coherent and incoherent propagation, faster energy transfer is uncovered in 2D nanoarrays than 1D chains, owing to availability of more numerous propagating channels in the 2D arrangement.

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Formally exact simulations of mesoscale exciton dynamics in molecular materials

Abstract: Excited state carriers, such as excitons, can diffuse on the 100 nm to micron length scale in molecular materials but only delocalize over short length scales due to coupling between...

Cited by 30 publications

References 82 publications

Calculating non-linear response functions for multi-dimensional electronic spectroscopy using dyadic non-Markovian quantum state diffusion

Calculating non-linear response functions for multi-dimensional electronic spectroscopy using dyadic non-Markovian quantum state diffusion

Computational spectroscopy of complex systems

Fully Quantum Modeling of Exciton Diffusion in Mesoscale Light Harvesting Systems

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