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  4. Evaluation of the importance of spin-orbit couplings in the nonadiabatic quantum dynamics with quantum fidelity and with its efficient “on-the-fly” ab initio semiclassical approximation
 
research article

Evaluation of the importance of spin-orbit couplings in the nonadiabatic quantum dynamics with quantum fidelity and with its efficient “on-the-fly” ab initio semiclassical approximation

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

We propose to measure the importance of spin-orbit couplings (SOCs) in the nonadiabatic molecular quantum dynamics rigorously with quantum fidelity. To make the criterion practical, quantum fidelity is estimated efficiently with the multiple-surface dephasing representation (MSDR). The MSDR is a semiclassical method that includes nuclear quantum effects through interference of mixed quantumclassical trajectories without the need for the Hessian of potential energy surfaces. Two variants of the MSDR are studied, in which the nuclei are propagated either with the fewest-switches surface hopping or with the locally mean field dynamics. The fidelity criterion and MSDR are first tested on one-dimensional model systems amenable to numerically exact quantum dynamics. Then, the MSDR is combined with “on-the-fly” computed electronic structure to measure the importance of SOCs and nonadiabatic couplings in the photoisomerization dynamics of CH2NH 2 considering 20 electronic states and in the collision of F + H2 considering six electronic states.

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Type
research article
DOI
10.1063/1.4738878
Web of Science ID

WOS:000312491400017

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

2012

Publisher

American Institute of Physics

Published in
Journal of Chemical Physics
Volume

137

Article Number

22A516

Subjects

spin-orbit couplings

•

nonadiabatic quantum dynamics

•

quantum fidelity

•

“on-the-fly” ab initio semiclassical approximation

URL

URL

http://jcp.aip.org/resource/1/jcpsa6/v137/i22/p22A516_s1
Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPT  
Available on Infoscience
August 10, 2012
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/84482
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