Assessing Nonadiabatic Dynamics Methods in Long Timescales - Archive ouverte HAL
Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2024

Assessing Nonadiabatic Dynamics Methods in Long Timescales

Résumé

Nonadiabatic dynamics simulations complement time-resolved experiments by revealing ultrafast excited-states mechanistic information in photochemical reactions. Understanding the relaxation mechanisms of photo-excited molecules finds application in energy, material, and medicinal research. However, with substantial computational costs, the nonadiabatic dynamics simulations have been restricted to ultrafast timescales, typically less than a few picoseconds, thus neglecting a wide range of photoactivated processes occurring in much longer timescales. Before developing new methodologies, we must ask: How well do the popular nonadiabatic dynamics methods perform in a long timescale simulation? In this study, we employ the multiconfiguration time-dependent Hartree (MCTDH) and its multilayer variants (ML-MCTDH), ab initio multiple spawning (AIMS), and fewestswitches surface hopping (FSSH) methodologies to simulate the excited-states dynamics of a weaklycoupled multidimensional Spin-Boson model Hamiltonian designed for a long timescale decay behavior. Our study assures that despite having very different theoretical backgrounds, all the above methods deliver qualitatively similar results. While quantum dynamics would be very costly for long timescale simulations, the trajectory-based approaches are paving the way for future advancements.
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jeudi 19 juin 2025
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Dates et versions

hal-04847340 , version 1 (19-12-2024)

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Saikat Mukherjee, Yorick Lassmann, Rafael S Mattos, Baptiste Demoulin, Basile F E Curchod, et al.. Assessing Nonadiabatic Dynamics Methods in Long Timescales. Journal of Chemical Theory and Computation, 2024, ⟨10.1021/acs.jctc.4c01349⟩. ⟨hal-04847340⟩
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