Implication of Sensitive Reactions to Ignition of Methyl Pentanoate:H-Abstraction Reactions by H and CH_(3) Radicals

作     者：SHANG Yanlei NING Hongbo SHI Jinchun LUO S.N. SHANG Yanlei;NING Hongbo;SHI Jinchun;LUO S.N

作者机构：Key Laboratory of Advanced Technologies of MaterialsMinistry of EducationSouthwest Jiaotong UniversityChengdu610031P.R.China The Peac Institute of Multiscale SciencesChengdu610027P.R.China 

出 版 物：《Chemical Research in Chinese Universities》 (高等学校化学研究（英文版）)

年 卷 期：2021年第37卷第3期

页      面：711-717页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：This work was supported by the National Natural Science Foundation of China(Nos.201903064 11627901) 

主　　题：Methyl pentanoate H-Abstraction Dual-level MS-T Ignition delay time Kinetic modeling 

摘      要：Methyl pentanoate(MP)was identified as a potential *** facilitate the application of MP with high efficiency in engines,a comprehensive understanding of combustion chemical kinetics of MP is *** this work,the H-abstraction reactions from MP by H and CH_(3) radicals,critical in controlling the initial fuel consumption,are theoretically investigated at the DLPNO-CCSD(T)/CBS(T-Q)//M06-2X/cc-pVTZ level of *** multistructural torsional(MS-T)anharmonicity is characterized using the dual-level MS-T method;the HF/3-21G and M06-2X/cc-pVTZ methods are chosen as the low-and high-level methods,*** conventional transition state theory(TST)is employed to calculate the high-pressure limit rate constants at 298-2000 K with the Eckart tunneling *** calculations indicate that the hydrogen atoms of the methylene functional group are easier to be abstracted by H and CH_(3) *** multistructural torsional anharmonicities of H-abstraction reactions MP+H/CH_(3) are significant within the temperature range *** tunneling effects are more pronounced at low temperatures,and contribute considerably to the rate constants below 500 *** model from the work of Diévart et *** updated with our calculations,and the simulations of the updated model are in excellent agreement with the reported ignition delay time of MP/O2/Ar and MP/Air *** sensitivity analysis indicates that the H-abstraction reactions,MP+H-CH_(3)CH_(2)CHCH_(2)C(-O)OCH_(3)/CH_(3)CHCH_(2)CH_(2)C(-O)OCH_(3)+H2,are critical in controlling the initial fuel consumption and ignition delay time of MP.