Theoretical Study of Abstraction and Addition Reactions of 2,4,4-Trimethyl-1-pentene with H and O(P-3) Radical
Theoretical Study of Abstraction and Addition Reactions of 2,4,4-Trimethyl-1-pentene with H and O(P-3) Radical
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2,4,4-三甲基-1-戊烯与H和O(P-3)自由基的抽象和加成反应的理论研究
DOI：
10.1021/acs.energyfuels.8b01917
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发表时间：
2018
期刊：
影响因子：
5.3
通讯作者：
Zuohua Huang
中科院分区：
文献类型：
--
作者：
Geyuan Yin;Erjiang Hu;Xiaojie Li;Jinfeng Ku;Zhenhua Gao;Zuohua Huang
用常规过渡态理论（TST）和正则变分过渡态理论（CVT）计算了2，4，4-三甲基-1-戊烯与H和O（3 P）的加成和萃取反应速率常数。在DLPNO-CCSD（T）/cc-pVTZ//M06-2X/6- 311 G（d，p）和CCSD（T）/6-311++G（d，p）//M06-2X/6-311（d，p）水平下计算了反应势能面。此外，量子力学效应是由多维小曲率隧道（SCT）和零曲率隧道（ZCT）方法确定的。2，4，4-三甲基-1-戊烯含有伯和仲烯丙基、烷基和乙烯基H原子。它还包含中心和末端碳原子通道的加成反应。结果表明，烯丙基型吸氢通道占主导地位的整体H提取所造成的较低的障碍。此外，一个自由基加入到末端碳主导的加成反应。在1500 K以上的抽氢反应中，分支率大于72%;在500 K以下的加成反应中，分支率大于90%。
The calculation of rate constants of addition and abstraction reactions of 2,4,4-trimethyl-1-pentene with H and O(3P) were conducted by conventional transition state theory (TST) and canonical variational transition state theory (CVT). Potential energy surfaces of reactions were calculated at the DLPNO–CCSD(T)/cc-pVTZ//M06-2X/6-311G(d,p) as well as the CCSD(T)/6-311++G(d,p)//M06-2X/6-311(d,p) level. Moreover, quantum mechanical effects were determined by multidimensional small-curvature tunneling (SCT) and zero-curvature tunneling (ZCT) methods. 2,4,4-Trimethyl-1-pentene contains primary and secondary allylic, alkylic, and vinylic H atoms. It also contains addition reactions into central and terminal carbon atom channels. The results indicated that allylic H abstraction channels dominate the overall H abstractions resulting from the lower barriers. In addition, a radical added into terminal carbon dominates the addition reactions. The branching ratio is more than 72% above 1500 K for H abstraction and more than 90% below 500 K for H addition reactions.