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Transition-event durations in one-dimensional activated processes.
- Source :
- Journal of Chemical Physics; 2/21/2007, Vol. 126 Issue 7, p074504, 18p, 11 Graphs
- Publication Year :
- 2007
-
Abstract
- Despite their importance in activated processes, transition-event durations—which are much shorter than first passage times—have not received a complete theoretical treatment. The authors therefore study the distribution ρ<subscript>b</subscript>(t) of durations of transition events over a barrier in a one-dimensional system undergoing overdamped Langevin dynamics. The authors show that ρ<subscript>b</subscript>(t) is determined by a Fokker-Planck equation with absorbing boundary conditions and obtain a number of results, including (i) the analytic form of the asymptotic short-time transient behavior, which is universal and independent of the potential function; (ii) the first nonuniversal correction to the short-time behavior leading to an estimate of a key physical time scale; (iii) following previous work, a recursive formulation for calculating, exactly, all moments of ρ<subscript>b</subscript> based solely on the potential function—along with approximations for the distribution based on a small number of moments; and (iv) a high-barrier approximation to the long-time (t→∞) behavior of ρ<subscript>b</subscript>(t). The authors also find that the mean event duration does not depend simply on the barrier-top frequency (curvature) but is sensitive to details of the potential. All of the analytic results are confirmed by transition-path-sampling simulations implemented in a novel way. Finally, the authors discuss which aspects of the duration distribution are expected to be general for more complex systems. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 126
- Issue :
- 7
- Database :
- Complementary Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 24101681
- Full Text :
- https://doi.org/10.1063/1.2434966