Zhang Yunju, Song Ruojing, Sun Yuxi, Sun Jingyu, Wang Rongshun
Key Laboratory of Photoinduced Functional Materials, Mianyang Normal University, Mianyang 621000, PR China.
Key Laboratory of Photoinduced Functional Materials, Mianyang Normal University, Mianyang 621000, PR China.
J Mol Graph Model. 2017 Sep;76:512-520. doi: 10.1016/j.jmgm.2017.05.001. Epub 2017 May 5.
Singlet and triplet potential energy surfaces for the CHO with I reaction have been investigated computationally to propose the reaction mechanisms and possible products. Multichannel RRKM theory and transition-state theory have been used to compute the overall and individual rate constants at 200-3000K and 10-10Torr. On the singlet PES, addition-elimination, substitution and H-abstraction mechanisms are located, and the addition-elimination mechanism is dominant. At 70Torr with N as bath gas, IM1(CHOOI) formed by collisional stabilization is dominated at 200-300K, whereas CHO and HIO are the major products at the temperatures between 350 and 3000K; The title reaction exhibits the typical falloff behavior. The results show that temperature and pressure affect the yield of products. Furthermore, the predicted rate constants at 298K 70Torr of N agree well with the available experimental values. On the triplet PES, the most favorable product should be CHI+O(Σ) at atmospheric condition. Other two pathways on the triplet PES will not compete with the pathways on the singlet PES in kinetically and thermodynamically.
已通过计算研究了CHO与I反应的单重态和三重态势能面，以提出反应机理和可能的产物。采用多通道RRKM理论和过渡态理论计算了200 - 3000K和10⁻¹⁰ - 10 Torr下的总速率常数和各速率常数。在单重态势能面上，确定了加成-消除、取代和氢提取机理，其中加成-消除机理占主导。在70 Torr以N作为缓冲气体时，通过碰撞稳定形成的IM1(CHOOI)在200 - 300K时占主导，而CHO和HIO在350至3000K的温度下是主要产物；该标题反应表现出典型的衰减行为。结果表明，温度和压力会影响产物的产率。此外，在298K、70 Torr的N条件下预测的速率常数与现有的实验值吻合良好。在三重态势能面上，在大气条件下最有利的产物应该是CHI + O(Σ)。三重态势能面上的其他两条路径在动力学和热力学上不会与单重态势能面上的路径竞争。
