Kinetics of H abstraction and addition reactions of 2,4,4-trimethyl-1-pentene by OH radical
Kinetics of H abstraction and addition reactions of 2,4,4-trimethyl-1-pentene by OH radical
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OH自由基对2,4,4-三甲基-1-戊烯的脱氢和加成反应动力学
DOI：
10.1016/j.fuel.2017.08.091
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发表时间：
2017-12
期刊：
影响因子：
7.4
通讯作者：
Zuohua Huang
中科院分区：
文献类型：
--
作者：
Geyuan Yin;Erjiang Hu;Feiyu Yang;Jinfeng Ku;Zuohua Huang
用正则变分过渡态理论和常规过渡态理论计算了2，4，4-三甲基-1-戊烯与OH的夺氢和OH加成反应的速率系数。在CCSD（T）/6-311++G（d，p）//BHANDHLYP/6-311（d，p）水平上计算了势能面，并采用一维Wigner方法和多维零曲率和小曲率隧道方法评估了量子效应。2，4，4-三甲基-1-戊烯含有伯烯丙基和仲烯丙基H提取、烷基和乙烯基H提取通道以及OH加成到中心和末端碳原子通道中。结果表明，烯丙基型吸氢通道是低势垒吸氢的主要通道，其中初级吸氢包括通过反应物络合物的间接吸氢通道和直接吸氢通道.此外，OH加成反应到中心和末端碳原子都包含货车德瓦尔斯反应物配合物，而后者的通道表现出负的温度依赖性作为其淹没的障碍的结果。在500 K以下的加成反应中，分支率大于75%;在1100 K以上的抽氢反应中，分支率大于80%。所有通道的速率系数拟合在一个准阿克里乌斯表达式。
The rate coefficients of H abstraction and OH addition reactions of 2,4,4-trimethyl-1-pentene with OH were determined by both canonical variational transition state theory and conventional transition state theory. The potential energy surfaces were calculated at CCSD(T)/6-311++G(d, p)//BHANDHLYP/6-311(d, p) level and quantum effects were evaluated by the one-dimensional Wigner method and the multidimensional zero-curvature and small-curvature tunneling methods. 2,4,4-Trimethyl-1-pentene contains primary and secondary allylic H abstraction, alkyl, and vinylic H abstraction channels and OH addition into central and terminal carbon atoms channels. The results show that allylic H abstraction channels dominate the overall H abstractions resulting from the lower barriers, in which, primary H abstraction involves indirect channel via a reactant complex and direct channel. Moreover, OH addition reactions into central and terminal carbon atoms all contain Van der Waals reactant complexes, while the latter channel exhibits negative temperature dependence as a result of its submerged barrier. The branching ratio is more than 75% for addition reactions below 500 K and more than 80% above 1100 K for H abstraction reactions. Rate coefficients of all channels were fitted in terms of a quasi-Arrhenius expression.
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影响因子：
2.8
作者：
C. Melius;R. Blint
通讯作者：
C. Melius;R. Blint
影响因子：
15
作者：
D. Truhlar;A. Kuppermann
通讯作者：
D. Truhlar;A. Kuppermann
DOI：
10.1002/chin.200703270
发表时间：
2007-01
期刊：
ChemInform
影响因子：
--
作者：
A. Fernández-Ramos;James A. Miller;S. Klippenstein;D. Truhlar
通讯作者：
A. Fernández-Ramos;James A. Miller;S. Klippenstein;D. Truhlar
影响因子：
2.9
作者：
Huynh, LK;Ratkiewicz, A;Truong, TN
通讯作者：
Truong, TN
影响因子：
4.4
作者：
CLOUTHIER, DJ;KAROLCZAK, J
通讯作者：
KAROLCZAK, J