采用凯莱传播子环聚合物分子动力学方法研究X + H₂插入反应（X = C(¹D)、N(²D)、O(¹D)、S(¹D)）的反应动力学。

Reactions dynamics for X + H2 insertion reactions (X = C(1D), N(2D), O(1D), S(1D)) with Cayley propagator ring-polymer molecular dynamics.

作者信息

Jiang Wenbin, Chen Yuhao, Li Yongle

机构信息

Department of Physics, International Center of Quantum and Molecular Structures, Shanghai University, Shanghai 200444, China.

Shanghai Key Laboratory of High Temperature Superconductors, Institute for Quantum Science and Technology, Shanghai University, Shanghai 200444, China.

出版信息

J Chem Phys. 2024 Jun 21;160(23). doi: 10.1063/5.0209143.

DOI:10.1063/5.0209143

PMID:38899683

Abstract

In this work, rate coefficients of four prototypical insertion reactions, X + H2 → H + XH (X = C(1D), N(2D), O(1D), S(1D)), and associated isotope reactions are calculated based on ring polymer molecular dynamics (RPMD) with Cayley propagator (Cayley-RPMD). The associated kinetic isotope effects are systematically studied too. The Cayley propagator used in this work increases the stability of numerical integration in RPMD calculations and also supports a larger evolution time interval, allowing us to reach both high accuracy and efficiency. So, our results do not only provide chemical kinetic data for the title reactions in an extended temperature range but also consist of experimental results, standard RPMD, and other theoretical methods. The results in this work also reflect that Cayley-RPMD has strong consistency and high reliability in its investigations of chemical dynamics for insertion reactions.

摘要

在这项工作中，基于具有凯莱传播子的环聚合物分子动力学（Cayley-RPMD），计算了四个典型插入反应X + H2 → H + XH（X = C(1D)、N(2D)、O(1D)、S(1D)）的速率系数以及相关的同位素反应。同时也系统地研究了相关的动力学同位素效应。本工作中使用的凯莱传播子提高了RPMD计算中数值积分的稳定性，并且支持更大的演化时间间隔，使我们能够达到高精度和高效率。因此，我们的结果不仅在扩展的温度范围内为标题反应提供了化学动力学数据，而且还与实验结果、标准RPMD以及其他理论方法相一致。这项工作的结果还表明，Cayley-RPMD在其对插入反应化学动力学的研究中具有很强的一致性和高可靠性。