Assessing Nonadiabatic Dynamics Methods in Long Timescales

2024/12/16 by Saikat Mukherjee, Yorick Lassmann, Rafael S. Mattos +3 · 1 voice · 11 citations
Chemistry · Physics and Astronomy · #Ab initio #Advanced Chemical Physics Studies #Excited state #Hamiltonian (control theory) #Hartree #Molecular spectroscopy and chirality #Physics #Picosecond #Quantum #Quantum dynamics #Quantum mechanics #Relaxation (psychology) #Spectroscopy and Quantum Chemical Studies #Statistical physics #Surface hopping

paper · open access · doi:10.1021/acs.jctc.4c01349

published in Journal of Chemical Theory and Computation 21(1), 29-37 (American Chemical Society)

openalex publication_date 2024/12/16 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/04

Abstract

Nonadiabatic dynamics simulations complement time-resolved experiments by revealing ultrafast excited-state mechanistic information in photochemical reactions. Understanding the relaxation mechanisms of photoexcited 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 fewest-switches surface hopping (FSSH) methodologies to simulate the excited-states dynamics of a weakly coupled 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.

Citations

• Simulation of Excitation by Sunlight in Mixed Quantum-Classical Dynamics
• Ab Initio Multiple Spawning: Photochemistry from First Principles Quantum Molecular Dynamics
• Dynamics of the dissipative two-state system
• MLatom Software Ecosystem for Surface Hopping Dynamics in Python with Quantum Mechanical and Machine Learning Methods

Cited by

• The Spin-MInt Algorithm: an Accurate and Symplectic Propagator for the Spin-Mapping Representation of Nonadiabatic Dynamics
• Perspective: Vibronic Coupling Potentials for Trajectory-Based Excited-State Dynamics
• Ehrenfest Dynamics with Spontaneous Localization
• On the electronic path integral normal modes of the Meyer-Miller-Stock-Thoss representation of nonadiabatic dynamics

Discussions

• Dynamics simulations of light-excited molecules are still a big challenge. If we need long timescales, comput. costs explode, and the methods available may not even work well. Here are the results of [bsky, 19 points, 1 comments]

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