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相空间中马尔可夫和非马尔可夫动力学的生存概率下界和近似首次穿越时间分布。

A lower bound to the survival probability and an approximate first passage time distribution for Markovian and non-Markovian dynamics in phase space.

机构信息

Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India.

出版信息

J Chem Phys. 2009 Dec 14;131(22):224504. doi: 10.1063/1.3269613.

Abstract

We derive a very general expression of the survival probability and the first passage time distribution for a particle executing Brownian motion in full phase space with an absorbing boundary condition at a point in the position space, which is valid irrespective of the statistical nature of the dynamics. The expression, together with the Jensen's inequality, naturally leads to a lower bound to the actual survival probability and an approximate first passage time distribution. These are expressed in terms of the position-position, velocity-velocity, and position-velocity variances. Knowledge of these variances enables one to compute a lower bound to the survival probability and consequently the first passage distribution function. As examples, we compute these for a Gaussian Markovian process and, in the case of non-Markovian process, with an exponentially decaying friction kernel and also with a power law friction kernel. Our analysis shows that the survival probability decays exponentially at the long time irrespective of the nature of the dynamics with an exponent equal to the transition state rate constant.

摘要

我们推导出了一个非常通用的表达式,用于描述在位置空间中的一个点处具有吸收边界条件的全相空间中执行布朗运动的粒子的生存概率和首次通过时间分布,该表达式与动力学的统计性质无关。该表达式与 Jensen 不等式一起,自然会得到实际生存概率的下界和近似首次通过时间分布。这些都可以用位置-位置、速度-速度和位置-速度方差来表示。这些方差的知识使我们能够计算生存概率的下界,从而计算首次通过分布函数。作为示例,我们针对高斯马尔可夫过程进行了计算,并且在非马尔可夫过程的情况下,还针对指数衰减摩擦核和幂律摩擦核进行了计算。我们的分析表明,生存概率在长时间内呈指数衰减,与动力学的性质无关,其指数等于过渡态速率常数。

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