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 of durations of transition events over a barrier in a one-dimensional system undergoing overdamped Langevin dynamics. The authors show that 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 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 behavior of . 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.
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21 February 2007
Research Article|
February 20 2007
Transition-event durations in one-dimensional activated processes
Bin W. Zhang;
Bin W. Zhang
Department of Physics and Astronomy,
University of Pittsburgh
, Pittsburgh, Pennsylvania 15260
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David Jasnow;
David Jasnow
a)
Department of Physics and Astronomy,
University of Pittsburgh
, Pittsburgh, Pennsylvania 15260
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Daniel M. Zuckerman
Daniel M. Zuckerman
b)
Department of Computational Biology, School of Medicine,
University of Pittsburgh
, Pennsylvania 15213
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a)
Electronic mail: [email protected]
b)
Electronic mail: [email protected]
J. Chem. Phys. 126, 074504 (2007)
Article history
Received:
September 25 2006
Accepted:
December 28 2006
Citation
Bin W. Zhang, David Jasnow, Daniel M. Zuckerman; Transition-event durations in one-dimensional activated processes. J. Chem. Phys. 21 February 2007; 126 (7): 074504. https://doi.org/10.1063/1.2434966
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