Oxidation of norbornadiene:Theoretical investigation on H-atom abstraction and related radical decomposition reactions

作     者：Jintao Chen Mingxia Liu Yuxiang Zhu Kairu Jin Zhenyu Tian Lijun Yang Chong-Wen Zhou 

作者机构：School of Energy and Power EngineeringBeihang UniversityBeijing 100191China Institute of Engineering ThermophysicsChinese Academy of SciencesBeijing 100190China University of Chinese Academy of SciencesBeijing 100049China School of AstronauticsBeihang UniversityBeijing 100191China Combustion Chemistry CentreSchool of Biological and Chemical SciencesUniversity of GalwayGalway H91TK33Ireland 

出 版 物：《Propulsion and Power Research》 (推进与动力（英文）)

年 卷 期：2023年第12卷第1期

页      面：104-113页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0807[工学-动力工程及工程热物理] 0802[工学-机械工程] 0703[理学-化学] 0825[工学-航空宇航科学与技术] 

基　　金：supported by the National Science and Technology Major Project(2017-Ⅲ-0004-0028/J2019-Ⅲ-0005-0048) NSFC(51976216) Sinopec Science and Technology Department the High-Performance Computing(HPC)Center of Beihang University 

主　　题：Norbornadiene Ab-initio calculations Rate constants Kinetic Thermochemistry 

摘      要：The chemical kinetics of hydrogen atom(H-atom)abstraction reactions from norbornadiene(NBD)by five radicals(H,O(^(3)P),OH,CH_(3),and HO_(2)),and the unimolecular reactions of three NBD derived radicals,were studied through high-level ab-initio *** geometries optimization and vibrational frequencies calculation for all the reactants,transition states,and products were obtained at the M06-2X/6-311ttG(d,p)level of *** zeropoint energy(ZPE)corrected potential energy surfaces(PESs)were determined at the QCISD(T)/cc-pVDZ,TZ level of theory with basis set corrections from MP2/cc-pVDZ,TZ,QZ methods for single point energy *** transition state theory(TST)was used for the rate constants calculations of H-atom abstraction reactions by five radicals(H,O(^(3)P),OH,CH_(3),and HO_(2))at temperatures from 298.15 to 2000 K,while the a-site H-atom abstraction reaction rate constant of NBD by OH radical has been obtained through variational transition state theory(VTST).The results show that the H-atom abstraction reactions from the α-carbon atom of NBD are the most critical channels at low *** rate constants for H-atom abstraction reactions by OH radical are also the fastest among all of the reaction channels investigated at the temperature range from 298.15 to 2000 ***-Ramsperger-Kassel-Marcus/Master Equation(RRKM/ME)has been used to calculate the pressure-and temperature-dependent rate constants for the unimolecular reactions of three related C7H7 product radicals which generated from H-atom abstraction reaction within temperature ranges of 300-2000 K and pressures of 0.01-100 atm.A combination of composite methods has been used to calculate the temperature-dependent thermochemical properties of NBD and related *** the calculated kinetics and thermochemistry data can be utilized in the model development for NBD oxidation.