skip to main content

Title: Communication: Global flux surface hopping in Liouville space

Recent years have witnessed substantial progress in the surface hopping (SH) formulation of non-adiabatic molecular dynamics. A generalization of the traditional fewest switches SH (FSSH), global flux SH (GFSH) utilizes the gross population flow between states to derive SH probabilities. The Liouville space formulation of FSSH puts state populations and coherences on equal footing, by shifting the hopping dynamics from Hilbert to Liouville space. Both ideas have shown superior results relative to the standard FSSH in Hilbert space, which has been the most popular approach over the past two and a half decades. By merging the two ideas, we develop GFSH in Liouville space. The new method is nearly as straightforward as the standard FSSH, and carries comparable computational expense. Tested with a representative super-exchange model, it gives the best performance among all existing techniques in the FSSH series. The obtained numerical results match almost perfectly the exact quantum mechanical solutions. Moreover, the results are nearly invariant under the choice of a basis state representation for SH, in contrast to the earlier techniques which exhibit notable basis set dependence. Unique to the developed approach, this property is particularly encouraging, because exact quantum dynamics is representation independent. GFSH in Liouville spacemore » significantly improves accuracy and applicability of SH for a broad range of chemical and physical processes.« less
Authors:
;  [1] ;  [2]
  1. Department of Chemistry, University of Southern California, Los Angeles, California 90089-1062 (United States)
  2. Department of Physics and Astronomy, University of Southern California, Los Angeles, California 90089-0485 (United States)
Publication Date:
OSTI Identifier:
22493241
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 19; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ACCURACY; COMPARATIVE EVALUATIONS; HILBERT SPACE; MAGNETIC SURFACES; MATHEMATICAL SOLUTIONS; MOLECULAR DYNAMICS METHOD; PERFORMANCE; PROBABILITY; QUANTUM MECHANICS; SURFACES