Temperature effects on singlet fission dynamics mediated by a conical intersection

Sun, Kewei; Xu, Quan; Chen, Lipeng; Gelin, Maxim F.; Zhao, Yue

doi:10.1063/5.0031435

Cited by 30 publications

(44 citation statements)

References 52 publications

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“…The off-diagonal elements representing the interaction between the ground and excited state are ∆ 12 = ∆ 21 = 0.32ω. It should be noted that, while similar single crystals, which include rubrene 52,53 and pentacene 54 have been modeled and investigated, the parameter values of the offdiagonal element of tetracene has not been well explored. Here we employ the value of pentacene as a representative case, while the interactions between the excited states are chosen to be ∆ 23 = ∆ 32 = 1.23ω for the pair 1 and ∆ 23 = ∆ 32 = 0.12ω for the pair 2, respectively.…”

Section: Resultsmentioning

confidence: 99%

Exciton Transfer in Organic Photovoltaic Cells: A Role of Local and Nonlocal Electron-Phonon Interactions in a Donor Domain

Cainelli,

Tanimura

2021

Preprint

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We theoretically investigate an exciton transfer process in a donor domain of organic photovoltaic cells focusing on the roles of local and nonlocal electron-phonon interactions.Our model consists of a three-level system described by the Holstein-Peierls Hamiltonian coupled to multiple heat baths for local and nonlocal molecular modes characterized by Brownian spectral distribution functions. We chose tetracene as a reference donor molecule, where the spectral distribution functions of the local and nonlocal modes exist.We then employ the reduced hierarchy equations of motion (HEOM) approach to simulating the dynamics of the system under the influence of the environment as a function of the electron-phonon coupling strength and temperature. We rigorously calculate the reduced density matrix elements to explain the timescale of dynamics under the influence of the dissipative local and nonlocal modes. The results indicate that the strong nonlocal electron-phonon interaction under high temperature conditions favors the exciton transfer process and enhances the efficiency of organic photovoltaic materials, while the lifetime of the exciton becomes shorter due to a low frequency local mode.

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Section: Resultsmentioning

confidence: 99%

Exciton Transfer in Organic Photovoltaic Cells: A Role of Local and Nonlocal Electron-Phonon Interactions in a Donor Domain

Cainelli,

Tanimura

2021

Preprint

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“…A small CT admixture can lead to an enhancement of low electronic coupling for singlet fission, while large CT components have also been found to play an important role in the spectra of crystals, aggregates, and light-harvesting complexes in photosynthetic apparatuses. Long-range corrected (LC) DFT is a good compromise for charge transfer characteristics, as illustrated in the tests of LC-DFTB by Darghouth et al 18 Other discussions on the CT components are seen in the works by Sun el al., 19 Balooch Qarai et al, 20 and others. 6,13,14,21 With electronic states obtained, Tölle et al 22 show how diabatic states can be defined and calculated, from which an excitonic model Hamiltonian can be built.…”

Section: B Excitons From First-principles Electronic Structure Theoriesmentioning

confidence: 99%

“…14,22 Various contributions in this Special Topic collection illustrate the flexibility and quantitative performance of vibronic exciton models that can be constructed from such multi-state descriptions. 19,20,24,25…”

Section: B Excitons From First-principles Electronic Structure Theoriesmentioning

confidence: 99%

“…Di Maiolo et al 25 show the promise of the ML-MCTDH method as a full quantum propagation scheme for hundreds of electronic states and vibrational modes, which is applied to coherent intra-chain exciton migration and the computation of temperature-dependent diffusion coefficients. Sun et al 19 employ a variational, multiconfigurational Davydov approach to probe the temperature dependence of singlet fission. Mixed quantum-classical nonadiabatic quantum dynamics approaches based on the QCLE are addressed by Kim and Rhee; 37 these can potentially be generalized for a large class of molecular systems but rely on certain kinds of approximations that become reasonable in the semiclassical or classical limits of nuclear degrees of freedom.…”

Section: E Quantum Dynamics Of Excitonsmentioning

confidence: 99%

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Excitons: Energetics and spatio-temporal dynamics

Jang,

Burghardt,

Hsu

et al. 2021

Preprint

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“…The method of displaced number states with the multi-D 2 Ansatz can provide efficient, quantitative descriptions of nonadiabatic dynamics at conical intersections in chemical reactions and beyond. 51,52 Based on many-body wave functions, the multiple Davydov Ansatz method is nonperturbative and numerically exact if provided sufficiently large multiplicities of the trial states, capable to compute nonlinear spectroscopic responses for close comparisons with experiment as will be elaborated in the next section. 52,127…”

Section: àπmentioning

confidence: 99%

The hierarchy of Davydov's Ansätze and its applications

Zhao

Sun

Chen

et al. 2021

WIREs Comput Mol Sci

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This review provides a bird's eye view over the development of the hierarchy of Davydov's Ansätze and its applications in a variety of problems in computational physical chemistry. Davydov's original solitons appeared in the 1970s as a candidate for vibrational energy carriers in proteins, thanks to their association with the Fröhlich Hamiltonian and the Holstein molecular crystal model.Momentum-space projection of those solitary waves emerged to be great approximations to the ground-state wave functions of the extended Holstein Hamiltonian, lending unambiguous evidence to the absence of formal quantum phase transitions in those systems. The multiple Davydov Ansätze are introduced, with increasing multiplicity, as incremental improvements of their corresponding single-Ansatz parents. The time-dependent variational formalism of Davydov's Ansätze is discussed in great detail, and the relative deviation of the Ansätze is constructed to quantify how faithfully they follow the Schrödinger equation, a quantity that is shown to vanish in the limit of large multiplicities. Three approaches to finite-temperature variational dynamics of Davydov's Ansätze are demonstrated, namely, the Monte Carlo importance sampling, the method of thermo-field dynamics, and the method of displaced number states. Applications of Davydov's Ansätze are given to variants of the spin-boson model, the Landau-Zener transition, the Holstein Hamiltonian, energy transfer in light-harvesting, and singlet fission in organic photovoltaics.As an example, simulation of multidimensional spectroscopic signals via Davydov's Ansätze is fully implemented for the finite-temperature fission process in crystalline rubrene.

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Temperature effects on singlet fission dynamics mediated by a conical intersection

Abstract: Note: This paper is part of the JCP Special Topic on Excitons: Energetics and Spatio Temporal Dynamics.

Cited by 30 publications

References 52 publications

Exciton Transfer in Organic Photovoltaic Cells: A Role of Local and Nonlocal Electron-Phonon Interactions in a Donor Domain

Exciton Transfer in Organic Photovoltaic Cells: A Role of Local and Nonlocal Electron-Phonon Interactions in a Donor Domain

Excitons: Energetics and spatio-temporal dynamics

The hierarchy of Davydov's Ansätze and its applications

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