On transition rates in surface hopping

Escartín JM, Romaniello P, Stella L, Reinhard PG, Suraud E (2012)

Publication Type: Journal article

Publication year: 2012

Journal

Journal of Chemical Physics AIP Publishing

Book Volume: 137

Article Number: 234113

Journal Issue: 23

DOI: 10.1063/1.4770280

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. © 2012 American Institute of Physics.

Authors with CRIS profile

Paul-Gerhard Reinhard Naturwissenschaftliche Fakultät

Involved external institutions

National Center for Scientific Research / Centre national de la recherche scientifique (CNRS) FR France (FR) European Theoretical Spectroscopy Facility (ETSF) BE Belgium (BE)

How to cite

APA:

Escartín, J.M., Romaniello, P., Stella, L., Reinhard, P.-G., & Suraud, E. (2012). On transition rates in surface hopping. Journal of Chemical Physics, 137(23). https://doi.org/10.1063/1.4770280

MLA:

Escartín, J. M., et al. "On transition rates in surface hopping." Journal of Chemical Physics 137.23 (2012).

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