Benchmarking the stochastic time-dependent variational approach for excitation dynamics in molecular aggregates

Chorošajev, Vladimir; Gelžinis, Andrius; Valkūnas, Leonas; Abramavičius, Darius

doi:10.1016/j.chemphys.2016.06.014

Cited by 9 publications

(10 citation statements)

References 67 publications

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“…The effective resonant coupling has been found to depend exponentially on the system-bath coupling strength. The time evolution of this relaxation has been revealed using the variational approach [34] and various polaron formation scenarios have been obtained. The SSE could be used to reveal the dynamical Hamiltonian as well, thus these effects are captured in the excitation dynamics presented in this paper.…”

Section: Discussionmentioning

confidence: 99%

“…One of the approximate approaches for the wavefunction is based on the smart guess of parametrized wavefunction (so-called ansatz). A variational method is then used to determine equations of motion for the wavefunction parameters [34][35][36][37] for the wavefunction to approximately satisfy the Schrödinger equation with. However, the solution is restricted to the specific domain of the ansatz.…”

Section: Introductionmentioning

confidence: 99%

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Excitation transfer pathways in excitonic aggregates revealed by the stochastic Schrödinger equation

Abramavicius

Abramavičius

2014

The Journal of Chemical Physics

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We derive the stochastic Schrödinger equation for the system wave vector and use it to describe the excitation energy transfer dynamics in molecular aggregates. We suggest a quantum-measurement based method of estimating the excitation transfer time. Adequacy of the proposed approach is demonstrated by performing calculations on a model system. The theory is then applied to study the excitation transfer dynamics in a photosynthetic pigment-protein Fenna-Matthews-Olson (FMO) aggregate using both the Debye spectral density and the spectral density obtained from earlier molecular dynamics simulations containing strong vibrational high-frequency modes. The obtained results show that the excitation transfer times in the FMO system are affected by the presence of the vibrational modes, however the transfer pathways remain the same.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Excitation transfer pathways in excitonic aggregates revealed by the stochastic Schrödinger equation

Abramavicius

Abramavičius

2014

The Journal of Chemical Physics

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“…By far the most widely used approximate approaches are based on the quantum master equation (QME) and the cumulant expansion. 1 , 3 , 8 − 15 Only recently the calculation of optical lineshapes has been approached using completely different methods—the time-dependent variational approach, 16 , 17 the density matrix renormalization group algorithm, 18 the reaction-coordinate master equation, 19 and the quantum–classical theory. 20 …”

Section: Introductionmentioning

confidence: 99%

Quantum–Classical Approach for Calculations of Absorption and Fluorescence: Principles and Applications

Braver

Valkūnas

Gelžinis

2021

J. Chem. Theory Comput.

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Absorption and fluorescence spectroscopy techniques provide a wealth of information on molecular systems. The simulations of such experiments remain challenging, however, despite the efforts put into developing the underlying theory. An attractive method of simulating the behavior of molecular systems is provided by the quantum–classical theory—it enables one to keep track of the state of the bath explicitly, which is needed for accurate calculations of fluorescence spectra. Unfortunately, until now there have been relatively few works that apply quantum–classical methods for modeling spectroscopic data. In this work, we seek to provide a framework for the calculations of absorption and fluorescence lineshapes of molecular systems using the methods based on the quantum–classical Liouville equation, namely, the forward–backward trajectory solution (FBTS) and the non-Hamiltonian variant of the Poisson bracket mapping equation (PBME-nH). We perform calculations on a molecular dimer and the photosynthetic Fenna–Matthews–Olson complex. We find that in the case of absorption, the FBTS outperforms PBME-nH, consistently yielding highly accurate results. We next demonstrate that for fluorescence calculations, the method of choice is a hybrid approach, which we call PBME-nH-Jeff, that utilizes the effective coupling theory [ Gelzinis A. Gelzinis A. 051103 32035455 J. Chem. Phys. 2020 152 ] to estimate the excited state equilibrium density operator. Thus, we find that FBTS and PBME-nH-Jeff are excellent candidates for simulating, respectively, absorption and fluorescence spectra of real molecular systems.

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“…(i) It became possible to include into “system” dozens of relevant quantum degrees of freedom and to evaluate the dynamics of such an extended system numerically exactly, assuming that the influence of the remaining quantum modes (the environment) can be neglected on the timescale of interest. This approach is represented by the multiconfiguration time‐dependent Hartree (MCTDH) method and its multilayer extension (ML‐MCTDH) as well as other variational basis set methods able to solve multidimensional Schrödinger equation.…”

Section: Introductionmentioning

confidence: 99%

“…The methods of the group (i) perform excellently at zero temperature. At room temperature, they require a statistical sampling of the initial conditions followed, in some procedures, by a double propagation in real and imaginary time . Recently, we have suggested an alternative and computationally efficient wave‐function‐based method for the simulation of time‐dependent properties of quantum systems with many degrees of freedom at finite temperature .…”

Section: Introductionmentioning

confidence: 99%

Thermal Schrödinger Equation: Efficient Tool for Simulation of Many‐Body Quantum Dynamics at Finite Temperature

Gelin

Borrelli

2017

Annalen der Physik

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We develop a wave-function-based method for the simulation of quantum dynamics of systems with many degrees of freedom at finite temperature. The method is inspired by the ideas of Thermo Field Dynamics (TFD). As TFD, our method is based on the doubling of the system's degrees of freedom and thermal Bogoliubov transformation. As distinct from TFD, our method implements the doubling of thermalized degrees of freedom only, and relies upon the explicitly constructed generalized thermal Bogoliubov transformation, which is not restricted to fermionic and bosonic degrees of freedom. This renders the present approach computationally efficient and applicable to a large variety of systems.

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Benchmarking the stochastic time-dependent variational approach for excitation dynamics in molecular aggregates

Cited by 9 publications

References 67 publications

Excitation transfer pathways in excitonic aggregates revealed by the stochastic Schrödinger equation

Excitation transfer pathways in excitonic aggregates revealed by the stochastic Schrödinger equation

Quantum–Classical Approach for Calculations of Absorption and Fluorescence: Principles and Applications

Thermal Schrödinger Equation: Efficient Tool for Simulation of Many‐Body Quantum Dynamics at Finite Temperature

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