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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ab Initio Studies of the Isomerization and Decomposition Reactions of the 1-Butoxy Radical
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Ab Initio Studies of the Isomerization and Decomposition Reactions of the 1-Butoxy Radical

机译：从头开始研究1-丁氧基自由基的异构化和分解反应

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摘要

The unimolecular reactions of the 1-butoxy radical, a prototype of atmospherically important alkoxy radicals, are studied. The structures of the isomers of the C_4H_9O radical and the transition structures of the isomerization and main decomposition reactions of 1-butoxy are determined by ab initio quantum chemical methods. The energy-dependent rate coefficients of the unimolecular reactions involved were obtained in RRKM calculations. The threshold energy for the fastest channel, the 1,5 intramolecular H-atom transfer is 8.12, 9.23, 9.16, and 9.51 kcal mol~(-1) according to the MP-SAC2, BAC-MP4, DFT, and an additively corrected MP4 method, respectively. For the β-C-C dissociation reaction we found a barrier of 16.03, 13.34, and 12.39 kcal mol~(-1) at the BAC-MP4, DFT, and additively corrected MP4 level. The barrier height for the 1,4 isomerization is close to that of the C-C bond rupture. The fastest reaction of the radical is isomerization involving a six-member transition structure, converting the alkoxy radical into an OH-substituted alkyl radical. The decomposition reaction can compete with the 1,5 isomerization step at high excitation or at combustion temperatures.
机译：研究了对大气重要的烷氧基自由基的原型1-丁氧基自由基的单分子反应。 C_4H_9O自由基的异构体的结构以及1-丁氧基的异构化和主要分解反应的过渡结构是通过从头算化学方法确定的。在RRKM计算中获得了所涉及的单分子反应的能量依赖性速率系数。根据MP-SAC2，BAC-MP4，DFT和累加校正后，最快通道的1,5,5分子内H原子转移的阈值能量为8.12、9.23、9.16和9.51 kcal mol〜（-1）。 MP4方法分别。对于β-C-C解离反应，我们在BAC-MP4，DFT和加成校正的MP4水平下发现了16.03、13.34和12.39 kcal mol〜（-1）的势垒。 1,4异构化的势垒高度接近C-C键断裂的高度。自由基的最快反应是异构化，涉及六元过渡结构，将烷氧基转化为OH取代的烷基。在高激发或燃烧温度下，分解反应可与1,5异构化步骤竞争。

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