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Theoretical Study on Mechanism and Kinetics of Reaction of O(3P) with Propane
Fu-qiang Jing,Jian-wei Cao,Xiao-jun Liu,Yu-feng Hu,Hai-tao Ma,Wen-sheng Bian
Author NameAffiliationE-mail
Fu-qiang Jing Key Laboratory of Luminescence and Optical Information, Ministry of Education, Beijing Jiaotong University, Beijing 100044, China;Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China  
Jian-wei Cao Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China  
Xiao-jun Liu Key Laboratory of Luminescence and Optical Information, Ministry of Education, Beijing Jiaotong University, Beijing 100044, China  
Yu-feng Hu Key Laboratory of Luminescence and Optical Information, Ministry of Education, Beijing Jiaotong University, Beijing 100044, China  
Hai-tao Ma Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China mht@iccas.ac.cn 
Wen-sheng Bian Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;University of Chinese Academy of Sciences, Beijing 100049, China bian@iccas.ac.cn 
Abstract:
The reaction of C3H8+O(3P)→C3H7+OH is investigated using ab initio calculation and dynamical methods. Electronic structure calculations for all stationary points are obtained using a dual-level strategy. The geometry optimization is performed using the unrestricted second-order Møller-Plesset perturbation method and the single-point energy is computed using the coupled-cluster singles and doubles augmented by a perturbative treatment of triple excitations method. Results indicate that the main reaction channel is C3H8+O(3P)→i-C3H7+OH. Based upon the ab initio data, thermal rate constants are calculated using the variational transition state theory method with the temperature ranging from 298 K to 1000 K. These calculated rate constants are in better agreement with experiments than those reported in previous theoretical studies, and the branching ratios of the reaction are also calculated in the present work. Furthermore, the isotope effects of the title reaction are calculated and discussed. The present work reveals the reaction mechanism of hydrogen-abstraction from propane involving reaction channel competitions is helpful for the under-standing of propane combustion.
Key words:  Reaction mechanism  Thermal rate constant  Variational transition state theory  Isotope effect
FundProject:This work is supported by the Chinese Min-istry of Science and Technology (No.2013CB834601), and the National Natural Science Foundation of China (No.21303217 and No.21473218), and Insti-tute of Chemistry, Chinese Academy of Sciences (No.20140160).
丙烷与O(3P)反应机理和动力学的理论研究
荆富强,曹剑炜,刘小君,胡煜峰,马海涛,边文生
摘要:
采用电子结构从头算和动力学方法研究了C3H8+O(3P)反应. 对该反应三重电子态上所有驻点的电子结构使用双水平从头算方法进行了深入的研究. 其中,采用UMP2/aug-cc-pVTZ方法和基组对各驻点进行了几何结构优化和频率分析,在相同计算水平上用内禀反应坐标(IRC)理论对最小能量途径(MEP)进行计算,并进行了详细的讨论,然后使用CCSD(T)/aug-cc-pVQZ方法和基组进行了单点能的校正.基于上述电子结构从头算的数据,采用变分过渡态理论方法在298~1000 K的温度范围内,对反应速率常数进行了深入的研究. 结果表明,丙烷和O(3P)反应的主要反应通道为C3H8+O(3P)→i-C3H7+OH. 与前人报道的理论研究结果相比,本文计算的反应速率常数与实验值更吻合. 此外,还对反应的产物分支比和同位素效应进行了详细的研究与讨论. 本文工作揭示了O(3P)从丙烷分子中抽取氢原子的反应机理及各反应通道之间的竞争关系,对理解丙烷的燃烧机理有很大的帮助,可为其它烃类分子的燃烧研究提供重要参考.
关键词:  反应机理  热速率常数  变分过渡态理论  同位素效应
DOI:10.1063/1674-0068/29/cjcp1603042
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