Nonadiabatic Excited-State Molecular Dynamics Methodologies: Comparison and Convergence

Victor M. Freixas, Alexander J. White, Tammie Nelson, Huajing Song, Dmitry V. Makhov, Dmitrii Shalashilin, Sebastian Fernandez-Alberti, Sergei Tretiak

Research output: Contribution to journalArticle

12 Citations (Scopus)


Direct atomistic simulation of nonadiabatic molecular dynamics is a challenging goal that allows important insights into fundamental physical phenomena. A variety of frameworks, ranging from fully quantum treatment of nuclei to semiclassical and mixed quantum-classical approaches, were developed. These algorithms are then coupled to specific electronic structure techniques. Such diversity and lack of standardized implementation make it difficult to compare the performance of different methodologies when treating realistic systems. Here, we compare three popular methods for large chromophores: Ehrenfest, surface hopping, and multiconfigurational Ehrenfest with ab initio multiple cloning (MCE-AIMC). These approaches are implemented in the NEXMD software, which features a common computational chemistry model. The resulting comparisons reveal the method performance for population relaxation and coherent vibronic dynamics. Finally, we study the numerical convergence of MCE-AIMC algorithms by considering the number of trajectories, cloning thresholds, and Gaussian wavepacket width. Our results provide helpful reference data for selecting an optimal methodology for simulating excited-state molecular dynamics.

Original languageEnglish
Pages (from-to)2970-2982
Number of pages13
JournalJournal of Physical Chemistry Letters
Issue number11
Publication statusPublished - 25 Mar 2021
Externally publishedYes


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