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Rate constants for diffusive processes by partial path sampling

2003/10/20 by Daniele Moroni, Peter G. Bolhuis, Titus S. van Erp · 2 citations
Physics and Astronomy · #cond-mat.stat-mech

paper · pdf · doi:10.1063/1.1644537

published as J. Chem. Phys. 120, 4055 (2004) · 12 pages, including 8 figures, RevTeX4

arxiv created 2003/10/20 · arxiv updated 2009/12/01

Abstract

We introduce a path sampling method for the computation of rate constants for systems with a highly diffusive character. Based on the recently developed algorithm of transition interface sampling (TIS) this procedure increases the efficiency by sampling only parts of complete transition trajectories confined within a certain region. The algorithm assumes the loss of memory for highly diffusive progression along the reaction coordinate. We compare the new technique to the TIS method for a simple diatomic system and show that the computation time of the new method scales linearly, instead of quadraticaly, with the length of the diffusive barrier. The validity of the memory loss assumption is also discussed.

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