Benchmarking various nonadiabatic semiclassical mapping dynamics methods with tensor-train thermo-field dynamics

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(2)

Published: July 9, 2024

Accurate quantum dynamics simulations of nonadiabatic processes are important for studies electron transfer, energy and photochemical reactions in complex systems. In this comparative study, we benchmark various approximate methods with mapping variables against numerically exact calculations based on the tensor-train (TT) representation high-dimensional arrays, including TT-KSL zero-temperature TT-thermofield finite-temperature dynamics. The investigated include mixed quantum–classical Ehrenfest mean-field fewest-switches surface hopping, linearized semiclassical dynamics, symmetrized quasiclassical spin-mapping method, extended classical models. Different model systems were evaluated, spin-boson condensed phase, linear vibronic coupling electronic transition through conical intersections, photoisomerization retinal, Tully’s one-dimensional scattering Our show that optimal choice dynamical method is system-specific, accuracy sensitively dependent zero-point-energy parameter initial sampling strategy variables.

Language: Английский

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Nonadiabatic Field: A Conceptually Novel Approach for Nonadiabatic Quantum Molecular Dynamics

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Reliable trajectory-based nonadiabatic quantum dynamics methods at the atomic/molecular level are critical for practical understanding and rational design of many important processes in real large/complex systems, where dynamical behavior electrons that nuclei coupled. The paper reports latest progress field (NaF), a conceptually novel approach with independent trajectories. Substantially different from mainstreams Ehrenfest-like surface hopping methods, nuclear force NaF involves arising coupling between electronic states, addition to adiabatic contributed by single state. is capable faithfully describing interplay motion broad regime, which covers relevant states keep coupled wide range or all time bifurcation characteristic essential. derived exact generalized phase space formulation coordinate-momentum variables, constraint (CPS) employed discrete electronic-state degrees freedom (DOFs) infinite Wigner used continuous DOFs. We propose efficient integrators equations both diabatic representations. Since formalism CPS not unique, can principle be implemented various representations correlation function (TCF) time-dependent property. They applied suite representative gas-phase condensed-phase benchmark models numerically results available comparison. It shown relatively insensitive representation TCF will potential tool reliable simulations mechanical transition systems.

Language: Английский

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Short-Range Coulomb Interaction Is a Key to Switch the Utilization of Higher Triplet Excitons in Multiresonance Thermally Activated Delayed Fluorescence Doped Film

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(46), P. 11562 - 11568

Published: Nov. 11, 2024

Multiresonance thermally activated delayed fluorescence (MR-TADF) materials have attracted widespread attention due to ultrahigh definition display standards. However, many MR-TADF lack TADF properties in both the solution and solid states. Interestingly, characteristics appear once these compounds are doped a suitable host film, but precise mechanism involved host-guest interaction remains uncertain. Herein, we systematically investigated role of interactions employing films (

Language: Английский

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PyCTRAMER: A Python package for charge transfer rate constant of condensed-phase systems from Marcus theory to Fermi’s golden rule

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(6)

Published: Aug. 9, 2024

In this work, we introduce PyCTRAMER, a comprehensive Python package designed for calculating charge transfer (CT) rate constants in disordered condensed-phase systems at finite temperatures, such as organic photovoltaic (OPV) materials. PyCTRAMER is restructured and enriched version of the CTRAMER (Charge-Transfer RAtes from Molecular dynamics, Electronic structure, Rate theory) [Tinnin et al. J. Chem. Phys. 154, 214108 (2021)], enabling computation Marcus CT constant six levels linearized semiclassical approximations Fermi’s golden rule (FGR) constant. It supports various types intramolecular intermolecular transitions excitonic states to state. Integrating quantum chemistry calculations, all-atom molecular dynamics (MD) simulations, spin-boson model construction, offers an automatic workflow handling photoinduced processes explicit solvent environments interfacial amorphous donor/acceptor blends. The also provides versatile tools individual steps, including electronic state analysis, state-specific force field MD construction energy trajectories. We demonstrate software’s capabilities through two examples, highlighting both prototypical OPV systems.

Language: Английский

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Charge Transfer Excitation of NeAr+ Ions in Collisions with Electrons

Atoms, Journal Year: 2024, Volume and Issue: 12(12), P. 67 - 67

Published: Dec. 12, 2024

We study the resonant processes of excitation weakly bound NeAr+ ions in collisions with free electrons Ne/Ar mixture plasma under conditions typical active media gas lasers and plasma-based UV radiation sources. The transitions leading to population charge transfer electronic terms are considered. Using an original theoretical approach developed recently, we dependences cross-sections several competing on incident electron energy temperature plasma. role continuous states internuclear motion is discussed. highlight specific features considered that stem from low binding demonstrate that, systems, efficiencies different channels differ greatly those obtained for moderate dissociation energies.

Language: Английский

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