Implementation of quasiclassical mapping approaches for nonadiabatic molecular dynamics in the PySurf package

Abstract

Quasiclassical methods for nonadiabatic molecular dynamics, based on the Mayer-Miller-Stock-Thoss mapping, are implemented in the open source computer package PySurf. This complements the implementation of surface hopping approaches performed in previous works, and leads to a unified code that allows nonadiabatic dynamics simulations using various mapping approaches (Ehrenfest dynamics, the linearized semiclassical initial value representation, the Poisson-bracket mapping equation, the “unity” approach for the indentity operator, the spin mapping, and the symmetrical quasiclassical windowing method) as well as different flavours of surface hopping (fewest-switches, Landau-Zener, and a mapping-inspired scheme). Furthermore, a plugin is developed to provide diabatic vibronic models in a sum-of-products form. This opens the way to the benchmark of different types of trajectory-based propagators on different models, against exact quantum dynamical simulations performed, e.g., by the multiconfigurational time-dependent Hartree method. Illustrative calculations, performed using the whole set of available propagators, are presented for different harmonic and anharmonic two-state models, exhibiting various degrees of correlation between vibrational modes.

Article information

Article type
Paper
Submitted
27 Mar 2025
Accepted
21 Jul 2025
First published
23 Jul 2025
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2025, Accepted Manuscript

Implementation of quasiclassical mapping approaches for nonadiabatic molecular dynamics in the PySurf package

D. Picconi, M. F. S. J. Menger, E. Palacino-González, E. X. Salazar and S. Faraji, Phys. Chem. Chem. Phys., 2025, Accepted Manuscript , DOI: 10.1039/D5CP01194A

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