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使用拉格朗日描述符检测反应岛及其与过渡路径采样的相关性。

Detecting reactive islands using Lagrangian descriptors and the relevance to transition path sampling.

作者信息

Patra Sarbani, Keshavamurthy Srihari

机构信息

Department of Chemistry, Indian Institute of Technology, Kanpur, U.P. 208 016, India.

出版信息

Phys Chem Chem Phys. 2018 Feb 14;20(7):4970-4981. doi: 10.1039/c7cp05912d.

Abstract

It has been known for sometime now that isomerization reactions, classically, are mediated by phase space structures called reactive islands (RI). RIs provide one possible route to correct for the nonstatistical effects in the reaction dynamics. In this work, we map out the reactive islands for the two dimensional Müller-Brown model potential and show that the reactive islands are intimately linked to the issue of rare event sampling. In particular, we establish the sensitivity of the so called committor probabilities, useful quantities in the transition path sampling technique, to the hierarchical RI structures. Mapping out the RI structure for high dimensional systems, however, is a challenging task. Here, we show that the technique of Lagrangian descriptors is able to effectively identify the RI hierarchy in the model system. Based on our results, we suggest that the Lagrangian descriptors can be useful for detecting RIs in high dimensional systems.

摘要

目前已经知道一段时间了,经典的异构化反应是由称为反应岛(RI)的相空间结构介导的。反应岛为校正反应动力学中的非统计效应提供了一条可能的途径。在这项工作中,我们绘制了二维穆勒-布朗模型势的反应岛,并表明反应岛与罕见事件采样问题密切相关。特别是,我们确定了所谓的反应概率(在过渡路径采样技术中有用的量)对分层反应岛结构的敏感性。然而,绘制高维系统的反应岛结构是一项具有挑战性的任务。在这里,我们表明拉格朗日描述符技术能够有效地识别模型系统中的反应岛层次结构。基于我们的结果,我们建议拉格朗日描述符可用于检测高维系统中的反应岛。

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