Towards a Theory of Transition Paths

  • Weinan E.
  • Eric Vanden-Eijnden
Article

Abstract

We construct a statistical theory of reactive trajectories between two pre-specified sets A and B, i.e. the portionsof the path of a Markov process during which the path makes a transition from A to B. This problem is relevant e.g. in the context of metastability, in which case the two sets A and B are metastable sets, though the formalism we propose is independent of any such assumptions on A and B. We show that various probability distributions on the reactive trajectories can be expressed in terms of the equilibrium distribution of the process and the so-called committor functions which give the probability that the process reaches first B before reaching A, either backward or forward in time. Using these objects, we obtain (i) the distribution of reactive trajectories, which gives the proportion of time reactive trajectories spend in sets outside of A and B; (ii) the hitting point distribution of the reactive trajectories on a surface, which measures where the reactive trajectories hit the surface when they cross it; (iii) the last hitting point distribution of the reactive trajectories on the surface; (iv) the probability current of reactive trajectories, the integral of which on a surface gives the net average flux of reactive trajectories across this surface; (v) the average frequency of reactive trajectories, which gives the average number of transitions between A and B per unit of time; and (vi) the traffic distribution of reactive trajectories, which gives some information about the regions the reactive trajectories visit regardless of the time they spend in these regions.

Key Words

Transition path theory transition state theory transition path sampling matastability reactive trajectories transition pathways 

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Copyright information

© Springer Science + Business Media, Inc. 2006

Authors and Affiliations

  • Weinan E.
    • 1
  • Eric Vanden-Eijnden
    • 2
  1. 1.Department of Mathematics and PACMPrinceton UniversityPrincetonUSA
  2. 2.Courant Institute of Mathematical SciencesNew York UniversityNew YorkUSA

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