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Fewest-switches with time uncertainty: A modified trajectory surface-hopping algorithm with better accuracy for classically forbidden electronic transitions

J. Chem. Phys. 116, 5424 (2002); doi:10.1063/1.1453404

Issue Date: 1 April 2002 | See: Erratum

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Ahren W. Jasper, Samuel N. Stechmann, and Donald G. Truhlar
Department of Chemistry and Supercomputer Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431
We present a modification of Tully's fewest-switches (TFS) trajectory surface-hopping algorithm (also called molecular dynamics with quantum transitions) that is called the fewest-switches with time uncertainty (FSTU) method. The FSTU method improves the self-consistency of the fewest-switches algorithm by incorporating quantum uncertainty into the hopping times of classically forbidden hops. This uncertainty allows an electronic transition that is classically forbidden at some geometry to occur by hopping at a nearby classically allowed geometry if an allowed hopping point is reachable within the Heisenberg interval of time uncertainty. The increased accuracy of the FSTU method is verified using a challenging set of three-body, two-state test cases for which accurate quantum-mechanical results are available. The FSTU method is shown to be more accurate than the TFS method in predicting total nonadiabatic quenching probabilities and product branching ratios. ©2002 American Institute of Physics.
History: Received 6 December 2001; accepted 4 January 2002
Permalink: http://link.aip.org/link/?JCPSA6/116/5424/1
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ERRATUM

  1. Erratum: "Fewest-switches with time uncertainty: A modified trajectory surface-hopping algorithm with better accuracy for classically forbidden electronic transitions" [J. Chem. Phys. 116, 5424 (2002)]
    Ahren W. Jasper et al.
    J. Chem. Phys. 117, 10427 (2002)

KEYWORDS and PACS

Keywords
PACS
  • 31.50.-x
    Electronic structure of atoms and molecules: theory Potential energy surfaces
  • 34.20.Mq
    Atomic and molecular collision processes and interactions Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions Potential energy surfaces for collisions
  • 82.20.Kh
    Physical chemistry and chemical physics Chemical kinetics and dynamics Potential energy surfaces for chemical reactions
  • YEAR: 2002

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

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