Assessing Nonadiabatic Dynamics Methods in Long Timescales

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.

Additional Resources

DOI: 10.1021/acs.jctc.4c01349

Bibtex:

@article{muk25assessing,
author = {Mukherjee, Saikat and Lassmann, Yorick and Mattos, Rafael S. and Demoulin, Baptiste and Curchod, Basile F. E. and Barbatti, Mario},
title = {Assessing Nonadiabatic Dynamics Methods in Long Timescales},
journal = {Journal of Chemical Theory and Computation},
volume = {21},
number = {1},
pages = {29-37},
year = {2025},
doi = {10.1021/acs.jctc.4c01349},
note ={PMID: 39680061},
URL = { https://doi.org/10.1021/acs.jctc.4c01349},
}