具有记忆的随机过程的不完全二元控制反应

T. Mendes, T. Guérin
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引用次数: 0

摘要

许多物理过程都受随机行走器到达目标所需的时间控制。在许多实际情况下,例如反应动力学,这个目标是不完美的:可能需要多次随机相遇才能真正触发反应。迄今为止,大多数关于不完全反应动力学的分析方法都局限于马尔可夫(无记忆)随机过程。然而,一旦随机漫步者与环境发生相互作用,其运动就会变成有效的非马尔可夫过程。在这里,我们提出了一种理论,它提供了非马尔可夫高斯随机漫步者在存在空间局部化反应速率或门控目标的情况下,在大凝聚体积中的平均反应时间。值得注意的是,在弱反应体系中,对于强亚二重性过程,我们的理论预测平均反应时间与反应受控时间的偏差与反应性呈非对称比例关系,我们通过分析确定了这一比例关系。这种效应说明了对目标的过去记忆如何影响下一次返回时间的统计,以及马尔可夫过程的差异性。该理论在一维和二维中得到了发展,并与随机模拟结果相吻合。这些结果让我们重新理解了非马尔可夫输运和局部反应性如何影响二输控制反应的动力学。
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Imperfect diffusion-controlled reactions for stochastic processes with memory
Many physical processes are controlled by the time that a random walker needs to reach a target. In many practical situations, such as reaction kinetics, this target is imperfect: multiple random encounters may be necessary to actually trigger a reaction. So far, most analytical approaches of imperfect reaction kinetics have been limited to Markovian (memoryless) stochastic processes. However, as soon as the random walker interacts with its environment, its motion becomes effectively non-Markovian. Here, we present a theory that provides the mean reaction time for a non-Markovian Gaussian random walker in a large confining volume in the presence of a spatially localized reaction rate or a gated target. Remarkably, in the weakly reactive regime, for strongly subdiffusive processes, our theory predicts that the deviation of the mean reaction time to the reaction controlled time displays a non-trivial scaling with the reactivity, which we identify analytically. This effect illustrates how the memory of past passages to the target influences the statistics of next-return times, to the difference of Markovian processes. The theory is developed in one and two dimensions and agrees with stochastic simulations. These results provide a refined understanding of how non-Markovian transport and local reactivity influence the kinetics of diffusion controlled reactions.
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