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  4. Measuring nonadiabaticity of molecular quantum dynamics with quantum fidelity and with its efficient semiclassical approximation
 
research article

Measuring nonadiabaticity of molecular quantum dynamics with quantum fidelity and with its efficient semiclassical approximation

Zimmermann, Tomas  
•
Vanicek, Jiri  
2012
Journal of Chemical Physics

We propose to measure nonadiabaticity of molecular quantum dynamics rigorously with the quantum fidelity between the Born-Oppenheimer and fully nonadiabatic dynamics. It is shown that this measure of nonadiabaticity applies in situations where other criteria, such as the energy gap criterion or the extent of population transfer, fail. We further propose to estimate this quantum fidelity efficiently with a generalization of the dephasing representation to multiple surfaces. Two variants of the multiple-surface dephasing representation (MSDR) are introduced, in which the nuclei are propagated either with the fewest-switches surface hopping or with the locally mean field dynamics (LMFD). The LMFD can be interpreted as the Ehrenfest dynamics of an ensemble of nuclear trajectories, and has been used previously in the nonadiabatic semiclassical initial value representation. In addition to propagating an ensemble of classical trajectories, the MSDR requires evaluating nonadiabatic couplings and solving the Schrödinger (or more generally, the quantum Liouville-von Neumann) equation for a single discrete degree of freedom. The MSDR can be also used in the diabatic basis to measure the importance of the diabatic couplings. The method is tested on three model problems introduced by Tully and on a two-surface model of dissociation of NaI.

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Type
research article
DOI
10.1063/1.3690458
Web of Science ID

WOS:000301664200008

Author(s)
Zimmermann, Tomas  
Vanicek, Jiri  
Date Issued

2012

Publisher

American Institute of Physics

Published in
Journal of Chemical Physics
Volume

136

Article Number

094106

Subjects

Classical Liouville Equation

•

Electronic-Transitions

•

Born-Oppenheimer

•

Schrodinger-Equation

•

Energy-Levels

•

Trajectories

•

Simulation

•

Surfaces

•

Spectra

•

Systems

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPT  
Available on Infoscience
March 5, 2012
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/78367
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