Mechanism and kinetic studies for OH radical-initiated atmospheric oxidation of methyl propionate
Mechanism and kinetic studies for OH radical-initiated atmospheric oxidation of methyl propionate
复制标题
OH自由基引发丙酸甲酯大气氧化的机理和动力学研究
DOI：
10.1016/j.atmosenv.2012.08.045
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发表时间：
2012-12
影响因子：
5
通讯作者：
Wang, Wenxing
中科院分区：
文献类型：
--
作者：
Hu, Yueming;Xu, Fei;Zhang, Qingzhu;Wang, Wenxing
通过 DFT 分子轨道理论计算研究了 OH 自由基引发的丙酸甲酯的大气氧化反应。在 B3LYP/6-31G(d,p) 水平上对反应物以及中间体、过渡态和产物进行几何优化。由于电子关联和基组效应，单点能量是通过使用不同层次的理论来计算的，包括二阶 Møller-Plesset 微扰理论 (MP2) 和单激发和双激发的耦合团簇理论，包括三激发的微扰校正 (CCSD(T))。详细的氧化机理被提出并讨论。结果表明，在一般大气条件下，3-氧代丙酸甲酯(HC(O)CH2C(O)OCH3)的形成在热力学上是可行的，并且烷氧基IM17(CH3CH(O)C(O)OCH3)的异构化很容易发生。使用小曲率隧道效应 (SCT) 贡献的规范变分过渡态 (CVT) 理论来预测速率常数。在 180–370 K 的可能大气温度范围内，确定了总体速率常数 k(T)(CH3CH2COOCH3+ OH)=(1.35 × 10−12)exp(−174.19/T) cm3molecule−1s−1。
DFT molecular orbital theory calculations were carried out to investigate OH radical-initiated atmospheric oxidation of methyl propionate. Geometry optimizations of the reactants as well as the intermediates, transition states and products were performed at the B3LYP/6-31G(d,p) level. As the electron correlation and basis set effect, the single-point energies were computed by using various levels of theory, including second-order Møller–Plesset perturbation theory (MP2) and the coupled-cluster theory with single and double excitations including perturbative corrections for the triple excitations (CCSD(T)). The detailed oxidation mechanism is presented and discussed. The results indicate that the formation of 3-oxo-methyl propionate (HC(O)CH2C(O)OCH3) is thermodynamically feasible and the isomerization of alkoxy radical IM17 (CH3CH(O)C(O)OCH3) can occur readily under the general atmospheric conditions. Canonical variational transition-state (CVT) theory with small curvature tunneling (SCT) contribution was used to predict the rate constants. The overall rate constants were determined, k(T)(CH3CH2COOCH3+ OH) = (1.35 × 10−12)exp(−174.19/T) cm3molecule−1s−1, over the possible atmospheric temperature range of 180–370 K.
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DOI：
10.1021/jp056117x
发表时间：
2006-01
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
A. Galano;A. Cruz-Torres;J. R. Álvarez-Idaboy
通讯作者：
A. Galano;A. Cruz-Torres;J. R. Álvarez-Idaboy
DOI：
10.1002/chin.197519099
发表时间：
1975-05
期刊：
ChemInform
影响因子：
--
作者：
J. Hine;P. Mookerjee
通讯作者：
J. Hine;P. Mookerjee
影响因子：
2.9
作者：
McGivern, WS;Suh, I;North, SW
通讯作者：
North, SW
DOI：
10.5860/choice.27-3319
发表时间：
1989
期刊：
--
影响因子：
--
作者：
T. Daubert;R. Danner
通讯作者：
T. Daubert;R. Danner
影响因子：
--
作者：
GARRETT, BC;TRUHLAR, DG
通讯作者：
TRUHLAR, DG