Rate Coefficients of Roaming Reaction H+MgH Using Ring Polymer Molecular Dynamics  

基于珠串分子动力学的漫游反应H+MgH的反应速率研究

作　　者：Hui Yang Wen-bin Fan Jun-hua Fang Jianing Song Yongle Li 杨慧;范文斌;方俊华;宋佳宁;李永乐(上海大学物理系,量子与分子结构国际中心,上海市高温超导重点实验室,上海200444;上海大学化学系,上海200444;美国加州理工学院化学与化工部,帕萨迪纳91125)

机构地区：[1]Department of Physics,International Center for Quantum and Molecular Structures,and Shanghai Key Laboratory of High Temperature Superconductors,Shanghai University,Shanghai 200444,China [2]Department of Chemistry,Shanghai University,Shanghai 200444,China [3]Devision of Chemistry and Chemical Engineering,California Institute of Technology,Pasadena 91125,USA

出　　处：《Chinese Journal of Chemical Physics》2021年第2期149-156,I0001,共9页化学物理学报（英文）

基　　金：supported by the National Natural Science Foundation of China(No.21503130 and No.11674212,and No.21603144);supported by the Young Eastern Scholar Program of the Shanghai Municipal Education Commission(QD2016021);the Shanghai Key Laboratory of High Temperature Superconductors(No.14DZ2260700);supported by Shanghai Sailing Program(No.2016YF1408400).

摘　　要：The ring-polymer molecular dynamics(RPMD)was used to calculate the thermal rate coefficients of the multi-channel roaming reaction H+MgH→Mg+H_(2).Two reaction channels,tight and roaming,are explicitly considered.This is a pioneering attempt of exerting RPMD method to multichannel reactions.With the help of a newly developed optimization-interpolation protocol for preparing the initial structures and adaptive protocol for choosing the force constants,we have successfully obtained the thermal rate coefficients.The results are consistent with those from other theoretical methods,such as variational transition state theory and quantum dynamics.Especially,RPMD results exhibit negative temperature dependence,which is similar to the results from variational transition state theory but different from the ones from ground state quantum dynamics calculations.

关 键 词：Ring-polymer molecular dynamics Semiclassical dynamics Multi-channel reaction Roaming reaction Reaction rate coefficient 

分 类 号：O643.11[理学—物理化学]