## Abstract

Trajectory surface hopping (TSH) is one of the most widely used quantum-classical algorithms for nonadiabatic molecular dynamics. Despite its empirical effectiveness and popularity, a rigorous derivation of TSH as the classical limit of a combined quantum electron-nuclear dynamics is still missing. In this work, we aim to elucidate the theoretical basis for the widely used hopping rules. Naturally, we concentrate thereby on the formal aspects of the TSH. Using a Gaussian wave packet limit, we derive the transition rates governing the hopping process at a simple avoided level crossing. In this derivation, which gives insight into the physics underlying the hopping process, some essential features of the standard TSH algorithm are retrieved, namely (i) non-zero electronic transition rate ("hopping probability") at avoided crossings; (ii) rescaling of the nuclear velocities to conserve total energy; (iii) electronic transition rates linear in the nonadiabatic coupling vectors. The well-known Landau-Zener model is then used for illustration. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4770280]

Original language | English |
---|---|

Article number | 234113 |

Number of pages | 6 |

Journal | Journal of Chemical Physics |

Volume | 137 |

Issue number | 23 |

DOIs | |

Publication status | Published - 21 Dec 2012 |

## Keywords

- energy level crossing
- molecular dynamics method
- potential energy surfaces
- quantum theory
- total energy
- wave functions
- NONADIABATIC MOLECULAR-DYNAMICS
- QUANTUM DECOHERENCE
- BORN-OPPENHEIMER
- SYSTEMS
- APPROXIMATION
- SIMULATIONS
- SCATTERING
- EVOLUTION