College of Chemistry and Material Science, Anhui Normal University, Wuhu 241000, China; State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Chinese Academy of Sciences Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Chinese Academy of Sciences Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
J Environ Sci (China). 2021 Jul;105:128-137. doi: 10.1016/j.jes.2020.12.029. Epub 2021 Jan 15.
The reaction mechanism and kinetics of the simplest Criegee intermediate CHOO reaction with hydroperoxymethyl formate (HPMF) was investigated at high-level quantum chemistry calculations. HPMF has two reactive functional groups, -C(O)OH and -OOH. The calculated results of thermodynamic data and rate constants indicated that the insertion reactions of CHOO with -OOH group of HPMF were more favorable than the reactions of CHOO with -C(O)OH group. The calculated overall rate constant was 2.33 × 10 cm/(molecule⋅sec) at 298 K and the rate constants decreased as the temperature increased from 200 to 480 K. In addition, we also proved the polymerization reaction mechanism between CHOO and -OOH of HPMF. This theoretical study interpreted the previous experimental results, and supplied the structures of the intermediate products that couldn't be detected during the experiment.
采用高精度量子化学计算方法研究了最简单的 Criegee 中间体 CHOO 与羟甲基氢过氧化物（HPMF）的反应机理和动力学。HPMF 具有两个反应性官能团：-C(O)OH 和 -OOH。热力学数据和速率常数的计算结果表明，CHOO 与 HPMF 的-OOH 基团的插入反应比 CHOO 与 -C(O)OH 基团的反应更有利。在 298 K 下，总速率常数为 2.33×10^-13 cm/(molecule·sec)，随着温度从 200 升高到 480 K，速率常数降低。此外，我们还证明了 CHOO 与 HPMF 的 -OOH 之间的聚合反应机理。该理论研究解释了以前的实验结果，并提供了实验中无法检测到的中间产物的结构。
