Tang Bo, Li Zhenyu
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China.
J Phys Chem A. 2020 Oct 15;124(41):8585-8593. doi: 10.1021/acs.jpca.0c06427. Epub 2020 Oct 6.
Criegee intermediates and alcohols are important species in the atmosphere. In this study, we use quantum chemistry and Born-Oppenheimer molecular dynamics (BOMD) simulations to investigate the reaction between methanol/ethanol and Criegee intermediates (- or -CHCHOO) in the gas phase and at the air-water interface. Reactions at the interface are found to be much faster than those in the gas phase. When water molecules are available, loop structures can be formed to facilitate the reaction. In addition, nonloop reaction pathways characterized by the formation of hydrated protons, although with a low possibility, are also identified at the air-water interface. Implications of our results on the fate of Criegee intermediates in the atmosphere are discussed, which deepen our understanding of Criegee intermediate-alcohol chemistry in humid environments.
克里吉中间体和醇类是大气中的重要物种。在本研究中，我们使用量子化学和玻恩-奥本海默分子动力学（BOMD）模拟来研究甲醇/乙醇与克里吉中间体（-或-CHCHOO）在气相和空气-水界面的反应。发现界面处的反应比气相中的反应快得多。当有水分子存在时，可以形成环状结构以促进反应。此外，在空气-水界面也发现了以水合质子形成为特征的非环状反应途径，尽管可能性较低。讨论了我们的结果对大气中克里吉中间体归宿的影响，这加深了我们对潮湿环境中克里吉中间体-醇类化学的理解。
