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The Journal of Chemical Physics
Article . 2012 . Peer-reviewed
Data sources: Crossref
https://dx.doi.org/10.48550/ar...
Article . 2013
License: arXiv Non-Exclusive Distribution
Data sources: Datacite
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On transition rates in surface hopping

Authors: Escartin, J. M.; Romaniello, P.; Stella, L.; Reinhard, P. -G.; Suraud, E.;

On transition rates in surface hopping

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.

Countries
Germany, United Kingdom
Keywords

potential energy surfaces, Surface Properties, QUANTUM DECOHERENCE, wave functions, FOS: Physical sciences, DDC Classification::5 Naturwissenschaften und Mathematik :: 53 Physik :: 530 Physik, Electrons, energy level crossing, Molecular Dynamics Simulation, 530, Phase Transition, SYSTEMS, Physics - Chemical Physics, SCATTERING, Computer Simulation, total energy, Chemical Physics (physics.chem-ph), BORN-OPPENHEIMER, quantum theory, NONADIABATIC MOLECULAR-DYNAMICS, SIMULATIONS, EVOLUTION, molecular dynamics method, Models, Chemical, Quantum Theory, Algorithms, APPROXIMATION

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
4
Average
Average
Average
Green
bronze