Development of semiclassical molecular dynamics simulation method.
Development of semiclassical molecular dynamics simulation method.
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DOI：
10.1039/c5cp07655b
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发表时间：
2016-04
期刊：
影响因子：
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通讯作者：
Hiroki Nakamura;S. Nanbu;Y. Teranishi;A. Ohta
中科院分区：
文献类型：
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作者：
Hiroki Nakamura;S. Nanbu;Y. Teranishi;A. Ohta
各种量子力学效应，如非绝热跃迁、量子力学隧道效应和相干性，在各种化学和生物系统中起着至关重要的作用。本文提出了一种将隧道效应纳入分子动力学（MD）方法的方法，该方法完全基于经典力学。沿着经典轨迹检测定义经典允许和禁止区域边界的焦散，并从每个合适的焦散出发确定作用最小的最佳隧道路径。与隧穿有关的实相也可以估计出来。为了帮助读者更好地理解本文提出的方法，文中还用一个简单的共线化学反应O + HCl→OH + Cl进行了数值演示。推广到动态从头开始的版本是相当直接的。用朱-中村理论处理锥形交点处的非绝热跃迁，可以发展出新的半经典MD方法。
Various quantum mechanical effects such as nonadiabatic transitions, quantum mechanical tunneling and coherence play crucial roles in a variety of chemical and biological systems. In this paper, we propose a method to incorporate tunneling effects into the molecular dynamics (MD) method, which is purely based on classical mechanics. Caustics, which define the boundary between classically allowed and forbidden regions, are detected along classical trajectories and the optimal tunneling path with minimum action is determined by starting from each appropriate caustic. The real phase associated with tunneling can also be estimated. Numerical demonstration with use of a simple collinear chemical reaction O + HCl → OH + Cl is presented in order to help the reader to well comprehend the method proposed here. Generalization to the on-the-fly ab initio version is rather straightforward. By treating the nonadiabatic transitions at conical intersections by the Zhu-Nakamura theory, new semiclassical MD methods can be developed.