2-Methyl-1-butanol (2M1B) is a favorable candidate of substitute fuels characterized with high energy density and low hygroscopicity. 2M1B radicals, which are the products of H-abstraction reactions of 2M1B, and their isomerization and decomposition reactions play a cardinal impact on the distribution of combustion products. In this work, the primary isomerization and decomposition reaction channels of 2M1B radicals were investigated by using QCISD(T)/CBS//M062x/cc-pVTZ and CBS-QB3 method, respectively. The accurate phenomenological temperature- and pressure-dependent rate constants covering temperatures of 250–2500 K and pressures from 1 × 10^–3 to 1 × 10³ bar along with high-pressure limit rate constants for these channels were computed by solving the RRKM/master equation. The calculations revealed that the isomerization reaction of RC2 → RC6 has the highest energy barrier among these reactions, while the decomposition reaction RC6 → CH₃CH₂CHCH₃ + CH₂O has the lowest energy barrier. Furthermore, the computed rate coefficients were also validated by using the previous pyrolysis experiment. The modeling results reproduce the experimental results satisfactorily. The current work not only provides reasonable kinetic data for the development of 2M1B combustion models but also lays a foundation to extend the kinetic mechanisms of alcohol with a longer chain.

中文翻译：

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2-甲基-1-丁醇自由基的异构化和分解反应的理论研究

2-甲基-1-丁醇（2M1B）是具有高能量密度和低吸湿性的代用燃料的良好候选者。2M1B的H-抽象反应产物2M1B自由基及其异构化和分解反应对燃烧产物的分布产生重要影响。在这项工作中，分别使用QCISD（T）/ CBS // M062x / cc-pVTZ和CBS-QB3方法研究了2M1B自由基的主要异构化和分解反应通道。精确的现象学依赖于温度和压力的速率常数，涵盖温度250至2500 K和压力1×10 ^–3至1×10 ³通过求解RRKM / master方程，计算出这些通道的bar以及高压极限速率常数。计算表明，在这些反应中，RC2→RC6的异构化反应能垒最高，而分解反应RC6→CH ₃ CH ₂ CHCH ₃ + CH ₂ O的能垒最低。此外，还使用先前的热解实验对计算出的速率系数进行了验证。建模结果令人满意地再现了实验结果。当前的工作不仅为开发2M1B燃烧模型提供了合理的动力学数据，而且为扩展具有较长链的醇的动力学机理奠定了基础。