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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Hydrogen abstraction from n-butanol by the hydroxyl radical: High level Ab initio study of the relative significance of various abstraction channels and the role of weakly bound intermediates
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Hydrogen abstraction from n-butanol by the hydroxyl radical: High level Ab initio study of the relative significance of various abstraction channels and the role of weakly bound intermediates

机译：通过羟基自由基从正丁醇中提取氢：各种提取通道的相对重要性以及弱结合中间体的作用的高水平从头算研究

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We have investigated the mechanism of the reaction of H abstraction from n-butanol by the hydroxyl radical (HO~·) using high level ab initio methods in conjunction with the correlation consistent basis sets up to quadruple-∫ quality (cc-pVQZ). This reaction is of significance in the atmosphere and combustion. The focus of the study has been on the relative importance of the abstractions from the specific n-butanol sites and on the role of reaction intermediates involved. Our results show that abstractions from the C_α and C_γ positions are kinetically most favored and nearly barrierless, with barrier height estimates of 0.10 and 0.47 kcal/mol, respectively, at the CCSD(T)/cc-pVQZ level. We have determined that the indicated barrier height order, C_α < C_γ < C_β < C_δ < OH, parallels that for the n-butanol bond dissociation energies established recently. The kinetically and thermodynamically most favored C_α abstraction occurs via a mechanism including the formation of the n-butanol?HO~· prereaction complex. The weakly bound postreaction complexes between the product radicals and H_2O have been identified for all the specific site abstraction reactions, with their calculated CCSD(T) binding energies of up to about 3 kcal/mol after correcting for the basis set superposition error. G3 method has been found to yield consistent results with those obtained from the CCSD(T) calculations for the predicted orders of both the H abstraction barrier heights and their exothermicities.
机译：我们已经使用高水平的从头算方法，结合相关一致的基础建立了高达4∫质量（cc-pVQZ）的方法，研究了由羟基自由基（HO〜·）从正丁醇中提取H的反应机理。该反应在大气和燃烧中是重要的。该研究的重点是从特定正丁醇位点提取的相对重要性以及所涉及的反应中间体的作用。我们的结果表明，从C_α和C_γ位置开始的抽象在动力学上是最受青睐的，并且几乎无障碍，在CCSD（T）/ cc-pVQZ水平下，障碍高度估计分别为0.10和0.47 kcal / mol。我们已经确定，所指示的势垒高度顺序C_α

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