Wang Rui, Wen Mingjie, Liu Shuai, Lu Yousong, Makroni Lily, Muthiah Balaganesh, Zhang Tianlei, Wang Zhiyin, Wang Zhuqing
School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, P. R. China.
Phys Chem Chem Phys. 2021 Jun 2;23(22):12749-12760. doi: 10.1039/d0cp00028k. Epub 2021 May 27.
The hydrolysis reaction of CHOO with water and water clusters is believed to be a dominant sink for the CHOO intermediate in the atmosphere. However, the favorable route for the hydrolysis of CHOO with water clusters is still unclear. Here global minimum searching using the Tsinghua Global Minimum program has been introduced to find the most stable geometry of the CHOO(HO) (n = 1-4) complex firstly. Then, based on these stable complexes, favorable hydrolysis of CHOO with (HO) (n = 1-4) has been investigated using the quantum chemical method of CCSD(T)-F12a/cc-pVDZ-F12//B3LYP/6-311+G(2d,2p) and canonical variational transition state theory with small curvature tunneling. The calculated results have revealed that, although the contribution of CHOO + (HO) is the most obvious in the hydrolysis of CHOO with (HO) (n = 1-4), the hydrolysis of CHOO with (HO) is not negligible in atmospheric gas-phase chemistry as its rate is close to the rate of the CHOO + HO reaction. The calculated results also show that, in a clean atmosphere, the CHOO + (HO) (n = 1-2) reaction competes well with the CHOO + SO reaction at 298 K when the concentrations of (HO) (n = 1-2) range from 20% relative humidity (RH) to 100% RH, and SO is 2.46 × 10 molecules per cm. Meanwhile, when the RH is higher than 40%, it is a new prediction that the CHOO + (HO) reaction can also compete well with the CHOO + SO reaction at 298 K. Besides, Born-Oppenheimer molecular dynamics simulation results show that all the favorable channels of the CHOO + (HO) (n = 1-3) reaction cannot react on a time scale of 100 ps in the NVT simulation. However, the NVE simulation results show that the CHOO + (HO) reaction can be finished well at 8.5 ps, indicating that the gas phase reaction of CHOO + (HO) is not negligible in the atmosphere. Overall, the present results have provided a definitive example of how the favorable hydrolysis of important atmospheric species with (HO) (n = 1-4) takes place, which will stimulate one to consider the favorable hydrolysis of water and water clusters with other Criegee intermediates and other important atmospheric species.
人们认为，CHOO与水及水团簇的水解反应是大气中CHOO中间体的主要汇。然而，CHOO与水团簇水解的有利途径仍不明确。本文首先引入使用清华全局最小值程序进行全局最小值搜索，以找到CHOO(HO)（n = 1 - 4）络合物的最稳定几何结构。然后，基于这些稳定的络合物，使用CCSD(T)-F12a/cc-pVDZ-F12//B3LYP/6-311+G(2d,2p)量子化学方法和含小曲率隧道效应的正则变分过渡态理论，研究了CHOO与(HO)（n = 1 - 4）的有利水解反应。计算结果表明，尽管在CHOO与(HO)（n = 1 - 4）的水解反应中CHOO + (HO)的贡献最为明显，但CHOO与(HO)的水解反应在大气气相化学中不可忽略，因为其反应速率接近CHOO + HO反应的速率。计算结果还表明，在清洁大气中，当(HO)（n = 1 - 2）的浓度范围从20%相对湿度（RH）到100%RH，且SO为2.46×10个分子每立方厘米时，在298K下CHOO + (HO)（n = 1 - 2）反应与CHOO + SO反应竞争激烈。同时，当RH高于40%时，这是一个新的预测，即在298K下CHOO + (HO)反应也能与CHOO + SO反应竞争激烈。此外，玻恩 - 奥本海默分子动力学模拟结果表明，在NVT模拟中，CHOO + (HO)（n = 1 - 3）反应的所有有利通道在100 ps的时间尺度内都无法发生反应。然而，NVE模拟结果表明，CHOO + (HO)反应在8.5 ps时可以顺利完成，这表明CHOO + (HO)的气相反应在大气中不可忽略。总体而言，目前的结果为重要大气物种与(HO)（n = 1 - 4）的有利水解反应如何发生提供了一个明确的例子，这将促使人们考虑水和水团簇与其他克里奇中间体及其他重要大气物种的有利水解反应。
