Towards a theory of transition paths

被引:332
作者
E, Weinan [1 ]
Vanden-Eijnden, Eric
机构
[1] Princeton Univ, Dept Math, Princeton, NJ 08544 USA
[2] Princeton Univ, PACM, Princeton, NJ 08544 USA
[3] NYU, Courant Inst Math Sci, New York, NY 10012 USA
基金
美国国家科学基金会;
关键词
transition path theory; transition state theory; transition path sampling; matastability; reactive trajectories; transition pathways;
D O I
10.1007/s10955-005-9003-9
中图分类号
O4 [物理学];
学科分类号
0702 ;
摘要
We construct a statistical theory of reactive trajectories between two pre-specified sets A and B, i.e. the portions of 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 oil 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.
引用
收藏
页码:503 / 523
页数:21
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