## Abstract

Mixed quantum-classical nonadiabatic dynamics is a widely used approach to simulate molecular dynamics involving multiple electronic states. There are two main categories of mixed quantum-classical nonadiabatic dynamics algorithms, namely, trajectory surface hopping (TSH) in which the trajectory propagates on a single potential energy surface, interrupted by hops, and self-consistent-potential (SCP) methods, such as semiclassical Ehrenfest, in which propagation occurs on a mean-field surface without hops. In this work, we will illustrate an example of severe population leaking in TSH. We emphasize that such leaking is a combined effect of frustrated hops and long-time simulations that drive the final excited-state population toward zero as a function of time. We further show that such leaking can be alleviated-but not eliminated-by the fewest switches with time uncertainty TSH algorithm (here implemented in the SHARC program); the time uncertainty algorithm slows down the leaking process by a factor of 4.1. The population leaking is not present in coherent switching with decay of mixing (CSDM), which is an SCP method with non-Markovian decoherence included. Another result in this paper is that we find very similar results with the original CSDM algorithm, with time-derivative CSDM (tCSDM), and with curvature-driven CSDM (κCSDM). Not only do we find good agreement for electronically nonadiabatic transition probabilities but also we find good agreement of the norms of the effective nonadiabatic couplings (NACs) that are derived from the curvature-driven time-derivative couplings as implemented in κCSDM with the time-dependent norms of the nonadiabatic coupling vectors computed by state-averaged complete-active-space self-consistent field theory.

Original language | English (US) |
---|---|

Pages (from-to) | 1672-1685 |

Number of pages | 14 |

Journal | Journal of Chemical Theory and Computation |

Volume | 19 |

Issue number | 6 |

DOIs | |

State | Published - Mar 28 2023 |

### Bibliographical note

Funding Information:This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0015997, by the National Natural Science Foundation of China (Award 21973053), and by the China Postdoctoral Science Foundation (2022M710032).

Publisher Copyright:

© 2023 American Chemical Society.

## PubMed: MeSH publication types

- Journal Article