基于实时路径积分的双分子化学反应动力学计算方法

doi:10.12066/j.issn.1007-2861.2312

摘要/Abstract

摘要：

化学反应速率常数、动力学同位素效应(kinetic isotope effect, KIE) 及散射截面的确定, 在燃烧、大气以及星际化学反应的化学动力学和动态学研究中起着不可或缺的作用. 而常用的理论如量子散射理论、过渡态理论(transition state theory, TST)和准经典轨线方法均难以准确快速地确定多原子反应的速率常数和散射截面. 近十几年来, 基于实时路径积分的珠串分子动力学(ring-polymer molecular dynamics, RPMD)方法在气相双分子化学反应动力学研究中的应用获得了成功. 而近几年来随着应用范围的扩大, RPMD方法在面临挑战的同时也取得了更多的研究进展.

关键词: 路径积分, 速率常数, 反应截面, 半经典

Abstract:

The determination of reaction rate coefficients and kinetic isotope effects (KIE) and measurement of cross-section are indispensable to the study of combustion, atmospheric, and interstellar chemical kinetics and dynamics. However, these parameters cannot be accurately and efficiently calculated by common theoretical methods such as quantum scattering, transition state theory (TST), and quasi-classical trajectory. In recent years, the ring-polymer molecular dynamics (RPMD) theory has been successfully applied for the investigation of gas-phase bimolecular reaction dynamics. Driven by modern advances, RPMD can also be implemented in many new applications. This work will review the present challenges of and recent advances in RPMD.

Key words: path integral, rate coefficient, reaction cross-section, semiclassical

中图分类号:

O643.11

李永乐, 范文斌, 任伟. 基于实时路径积分的双分子化学反应动力学计算方法[J]. 上海大学学报(自然科学版), 2022, 28(5): 896-907.

LI Yongle, FAN Wenbin, REN Wei. Dynamic calculation method of bimolecular chemical reaction based on real-time path integral[J]. Journal of Shanghai University（Natural Science Edition）, 2022, 28(5): 896-907.

图/表 1

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