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平衡态下单向通量、牵连度和首次穿越及跃迁路径时间之间的关系。

Relations among Unidirectional Fluxes at Equilibrium, Committors, and First Passage and Transition Path Times.

机构信息

Section of Molecular Transport, Eunice Kennedy Shriver National Institute of Child Health and Human development, National Institutes of Health, Bethesda, Maryland 20892, United States.

Laboratory of Chemical Physics, National institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, Maryland 20892, United States.

出版信息

J Phys Chem B. 2022 Sep 8;126(35):6624-6628. doi: 10.1021/acs.jpcb.2c03757. Epub 2022 Aug 29.

Abstract

For multidimensional diffusive dynamics, we algebraically derive remarkable analytical expressions that relate the mean first passage and transition path times between two dividing surfaces with the number of unidirectional transitions per unit time (fluxes) at equilibrium between the two surfaces and the committor (the probability of reaching one surface before the other). In one dimension, such relationships can be easily derived because analytical expressions for all the above-mentioned quantities can be found. This is not possible in higher dimensions, and at first sight, the problem seems much harder. We circumvent the difficulty that the equations determining the mean first passage and transition path times cannot be solved analytically by multiplying these equations by the committor, integrating both sides and finally using the divergence theorem. A byproduct of our derivation is an analytical expression for the starting point distribution over which individual first passage and transition path times must be averaged. It turns out that this distribution is not the Boltzmann one, but it has a simple physical interpretation.

摘要

对于多维扩散动力学,我们推导出了显著的解析表达式,这些表达式将两个分割面之间的平均首次通过时间和转移路径时间与两个面之间的平衡状态下每个单位时间的单向跃迁次数(通量)以及连接度(在另一个面之前到达一个面的概率)联系起来。在一维情况下,由于可以找到所有上述量的解析表达式,因此可以很容易地推导出这样的关系。在更高维度上则不行,乍一看,这个问题似乎要困难得多。我们通过将确定平均首次通过时间和转移路径时间的方程乘以连接度来规避方程不能解析求解的困难,对两边积分,最后使用散度定理。我们的推导的一个副产品是关于单个首次通过时间和转移路径时间必须平均的起点分布的解析表达式。事实证明,该分布不是玻尔兹曼分布,但是它具有简单的物理解释。

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