Unimolecular Decomposition of Ethyl Hydroperoxide: Ab Initio/Rice-Ramsperger-Kassel-Marcus Theoretical Prediction of Rate Constants

被引：20

作者：

Chen, Dongna ^{[1
]}

Jin, Hanfeng ^{[1
]}

Wang, Zhandong ^{[1
]}

Zhang, Lidong ^{[1
]}

Qi, Fei ^{[1
,2
]}

机构：

[1] Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Anhui, Peoples R China

[2] Univ Sci & Technol China, State Key Lab Fire Sci, Hefei 230026, Anhui, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2011年 / 115卷 / 05期

关键词：

DENSITY-FUNCTIONAL THERMOCHEMISTRY; EVALUATED KINETIC-DATA; GAS-PHASE ACIDITY; ROTATION BARRIERS; UPPER TROPOSPHERE; PEROXY-RADICALS; PHOTOELECTRON-SPECTROSCOPY; ALKYL HYDROPEROXIDES; MECHANISMS; BOND;

D O I：

10.1021/jp1099305

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Alkyl hydropercuddes 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-O 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 x 10(52)T(-11.91)exp(-26879/T) s(-1) at 1 atm. The rate constants of the reaction CH3CH2OOH -> CH3CH2O + OH at different temperatures and pressures have been calculated, which can help us to comprehend the reactions of CH3CH2OOH at experimental conditions.

引用

页码：602 / 611

页数：10

共 33 条

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JOURNAL OF CHEMICAL PHYSICS, 2006, 125 (13):
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[33] A combined crossed beam and ab initio investigation on the reaction of carbon species with C4H6 isomers.: III.: 1,2-butadiene, H2CCCH(CH3) (X1A′) -: a non-Rice-Ramsperger-Kassel-Marcus system?
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