Unimolecular Decomposition of Ethyl Hydroperoxide: Ab Initio/Rice鈭扲amsperger鈭扠assel鈭扢arcus Theoretical Prediction of Rate Constants

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• 作者：Dongna Chen ; Hanfeng Jin ; Zhandong Wang ; Lidong Zhang ; Fei Qi
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：February 10, 2011
• 年：2011
• 卷：115
• 期：5
• 页码：602-611
• 全文大小：1094K
• 年卷期：v.115,no.5(February 10, 2011)
• ISSN：1520-5215

文摘

Alkyl hydroperoxides are found to be important intermediates in the combustion and oxidation processes of hydrocarbons. However, studies of ethyl hydroperoxide (CH₃CH₂OOH) are limited. In this work, kinetics and mechanisms for unimolecular decomposition of CH₃CH₂OOH have been investigated. The potential energy surface of decomposition reactions have first been predicted at the CCSD(T)/6-311+G(3df,2p)//B3LYP/6-311G(d,p) level. The results show that the formation of CH₃CH₂O + OH via O鈭扥 direct bond dissociation is dominant, the branching ratio of which is over 99% in the whole temperature range from 300 to 1000 K, and its rate constant can be expressed as k1 = 9.26 脳 10⁵²T^鈭?1.91exp(鈭?6879/T) s^鈭? at 1 atm. The rate constants of the reaction CH₃CH₂OOH 鈫?CH₃CH₂O + OH at different temperatures and pressures have been calculated, which can help us to comprehend the reactions of CH₃CH₂OOH at experimental conditions.