当前位置：
X-MOL 学术
›
ACS Earth Space Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Theoretical Investigation of the Atmospheric Cl Oxidation Chemistry of 4-Methyl-3-penten-2-one
ACS Earth and Space Chemistry ( IF 2.9 ) Pub Date : 2020-08-18 , DOI: 10.1021/acsearthspacechem.0c00169 Yan Zhao 1 , Kunling Han 1 , Xiubiao Ma 1
ACS Earth and Space Chemistry ( IF 2.9 ) Pub Date : 2020-08-18 , DOI: 10.1021/acsearthspacechem.0c00169 Yan Zhao 1 , Kunling Han 1 , Xiubiao Ma 1
Affiliation
|
The reaction mechanisms and kinetics of 4-methyl-3-penten-2-one (MPO) with atomic Cl have been studied using second-order Møller–Plesset perturbation theory (MP2) and canonical variational transition-state (CVT) theory with small-curvature tunneling (SCT) correction methods. Eight different reaction paths are considered: two possible Cl addition reactions and six possible hydrogen abstraction reactions. The results of the theoretical investigation indicate that Cl addition dominates the initial reactions of MPO with Cl atoms, and the most energetically favorable pathway is the Cl addition to the double bond carbon adjacent to the carbonyl in the molecule. Among all of the six H-abstraction paths, the H abstraction from the two methyl groups linked to the double bond is predicted to occur readily according to the calculated data. In addition, the 1,5-H shift isomerization process, involving the Cl addition mechanism, was proposed and found to be feasible. The major possible products that were detected in experiment and derived from our theoretical study have been identified. The rate constants and branching ratios of the main reaction paths have been obtained over the temperature range of 180–380 K. The total rate constants are dependent on temperature and the Arrhenius equation is fitted as ktotal = (2.99 × 10–13)exp(1795.60/T). The atmospheric lifetime is also estimated and shows a positive temperature dependence.
中文翻译：
4-甲基-3-戊烯-2-酮的大气Cl氧化化学反应的理论研究
使用二阶Møller-Plesset微扰理论（MP2）和典型的变分过渡态（CVT）理论研究了4-甲基-3-戊烯-2-酮（MPO）与原子Cl的反应机理和动力学。曲率隧穿（SCT）校正方法。考虑了八种不同的反应路径：两个可能的Cl加成反应和六个可能的氢提取反应。理论研究的结果表明，Cl加成在MPO与Cl原子的初始反应中占主导地位，而最有力的有利途径是Cl加成到与分子中羰基相邻的双键碳上。在所有六个H吸收路径中，根据计算数据，预测很容易从连接到双键的两个甲基中提取H。另外，1 提出了涉及Cl加成机理的5-H转移异构化方法，并认为是可行的。已经确定了在实验中检测到并从我们的理论研究中得出的主要可能产物。在180–380 K的温度范围内获得了主要反应路径的速率常数和支化比。总速率常数取决于温度，并且将Arrhenius方程拟合为k total =（2.99×10 –13）exp（1795.60 / T）。还估算了大气寿命，并显示出正温度依赖性。
更新日期：2020-08-18
中文翻译：
4-甲基-3-戊烯-2-酮的大气Cl氧化化学反应的理论研究
使用二阶Møller-Plesset微扰理论（MP2）和典型的变分过渡态（CVT）理论研究了4-甲基-3-戊烯-2-酮（MPO）与原子Cl的反应机理和动力学。曲率隧穿（SCT）校正方法。考虑了八种不同的反应路径：两个可能的Cl加成反应和六个可能的氢提取反应。理论研究的结果表明，Cl加成在MPO与Cl原子的初始反应中占主导地位，而最有力的有利途径是Cl加成到与分子中羰基相邻的双键碳上。在所有六个H吸收路径中，根据计算数据，预测很容易从连接到双键的两个甲基中提取H。另外，1 提出了涉及Cl加成机理的5-H转移异构化方法，并认为是可行的。已经确定了在实验中检测到并从我们的理论研究中得出的主要可能产物。在180–380 K的温度范围内获得了主要反应路径的速率常数和支化比。总速率常数取决于温度，并且将Arrhenius方程拟合为k total =（2.99×10 –13）exp（1795.60 / T）。还估算了大气寿命，并显示出正温度依赖性。
京公网安备 11010802027423号