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

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

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

机构地区：[1]School of Energy and Power Engineering,Beihang University,Beijing 100191,China [2]Institute of Engineering Thermophysics,Chinese Academy of Sciences,Beijing 100190,China [3]University of Chinese Academy of Sciences,Beijing 100049,China [4]School of Astronautics,Beihang University,Beijing 100191,China [5]Combustion Chemistry Centre,School of Biological and Chemical Sciences,University of Galway,Galway H91TK33,Ireland

出　　处：《Propulsion and Power Research》2023年第1期104-113,共10页推进与动力（英文）

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.

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 calculations.The 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 theory.The 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 calculations.Conventional 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 temperatures.Total 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 K.Rice-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 radicals.All the calculated kinetics and thermochemistry data can be utilized in the model development for NBD oxidation.

关 键 词：NORBORNADIENE Ab-initio calculations Rate constants KINETIC THERMOCHEMISTRY 

分 类 号：O64[理学—物理化学]