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Algorithmic decoherence time for decay-of-mixing non–Born–Oppenheimer dynamics

J. Chem. Phys. 129, 024112 (2008); doi:10.1063/1.2948395

Published 11 July 2008

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Shu Chun Cheng,1 Chaoyuan Zhu,1 Kuo Kan Liang,2 Sheng Hsien Lin,1,2,3 and Donald G. Truhlar4
1Department of Applied Chemistry, Institute of Molecular Science and Center for Interdisciplinary Molecular Science, National Chiao-Tung University, Hsinchu 300, Taiwan
2Division of Mechanics, Research Center for Applied Sciences, Academia Sinica, Taipei 115, Taiwan
3Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan
4Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455-0431, USA
The performance of an analytical expression for algorithmic decoherence time is investigated for non–Born–Oppenheimer molecular dynamics. There are two terms in the function that represents the dependence of the decoherence time on the system parameters; one represents decoherence due to the quantum time-energy uncertainty principle and the other represents a back reaction from the decoherent force on the classical trajectory. We particularly examine the question of whether the first term should dominate. Five one-dimensional two-state model systems that represent limits of multidimensional nonadiabatic dynamics are designed for testing mixed quantum-classical methods and for comparing semiclassical calculations with exact quantum calculations. Simulations are carried out with the semiclassical Ehrenfest method (SE), Tully's fewest switch version (TFS) of the trajectory surface hopping method, and the decay-of-mixing method with natural switching, coherent switching (CSDM), and coherent switching with reinitiation (CSDM-D). The CSDM method is demonstrated to be the most accurate method, and it has several desirable features: (i) It behaves like the representation-independent SE method in the strong nonadiabatic coupling regions; (ii) it behaves physically like the TFS method in noninteractive region; and (iii) the trajectories are continuous with continuous momenta. The CSDM method is also demonstrated to balance coherence well with decoherence, and the results are nearly independent of whether one uses the adiabatic or diabatic representation. The present results provide new insight into the formulation of a physically correct decoherence time to be used with the CSDM method for non–Born–Oppenheimer molecular dynamic simulations. ©2008 American Institute of Physics
History: Received 29 February 2008; accepted 28 May 2008; published 11 July 2008
Permalink: http://link.aip.org/link/?JCPSA6/129/024112/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.10.+z
    Theory of electronic structure, electronic transitions, and chemical binding in atoms and molecules
  • 31.15.xv
    Molecular dynamics and other numerical methods in atomic and molecular physics
  • 03.65.Yz
    Decoherence; open systems; quantum statistical methods
  • 03.65.Sq
    Semiclassical theories and applications in quantum mechanics
  • YEAR: 2008

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0021-9606 (print)   1089-7690 (online)
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