Computational study of the reaction mechanism and kinetics of ethyl acrylate ozonolysis in atmosphere

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• 作者：Yanhui Sun ; Haijie Cao ; Dandan Han ; Jing Li ; Maoxia He ; ^{hemaox@sdu.edu.cn} ; Chen Wang
• 关键词：Ethyl acrylate (EA) ; Reaction mechanism ; Kinetic study ; Quantum chemical method
• 刊名：Chemical Physics
• 出版年：2012
• 期刊代码：18_03010104
• 类别：ch
• 出版时间：19 June, 2012
• 卷：402
• 期：Complete
• 页码：6-13
• 文件大小：774 K

摘要

The reaction mechanism for the ozonolysis of ethyl acrylate (EA) has been investigated at the CCSD(T)/6-31G(d)+CF//B3LYP/6-31+G(d,p) level of theory. The profile of the potential energy surface (PES) is constructed. Ozone adds to EA via a cyclic transition state to produce a highly unstable primary ozonide which can decompose readily. Over the temperature range of 200-2000 K, the total and individual rate constants are obtained by employing multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The calculated rate constants are 1.37 脳 10^鈭?8 cm³ molecule^鈭? s^鈭? at 294 K and 1.65 脳 10^鈭?8 cm³ molecule^鈭? s^鈭? at 298 K under the pressure of 760 Torr. The main products of the reactions are ethyl glyoxylate and formaldehyde. These results are in good agreement with the previous experimental data. Several experimental uncertain products are identified. The branching ratios of main reaction paths are also discussed at different temperatures and pressures.