The kinetic chemistry of H-abstraction reactions of isobutene by the OH radical and the channels of the C₄H₉O complex formed by addition of the hydroxyl to isobutene were investigated in current work. Their rate constants at high pressure limits were computed based on the canonical transition state theory with tunneling effect considered, following the construction of the potential energy surface (PES) based on a duel-level quantum chemistry method at CCSD(T) /CBS// BHandHLYP/6-311G(d,p) level. Comparison of reaction rate constants of H-abstractions by the OH radical for isobutene with those for propene and 3-hexene in the literature showed differences of less than factor 6. Isomerization pathways of the hydroxybutyl radicals to each other and to the isobutoxy radical were discussed in details. It was observed that the rate constants for both H-abstraction and isomerization via H-transfer were improved by considering tunneling effect. Subsequently, the pressure-dependent rate constants of multiple channels for each hydroxybutyl radical and of the dominant channel for isobutoxy radical were calculated based on RRKM/ME theory. The effect of chemical activation and thermal initial distribution was discussed with the case of 2-hydroxymethyl-prop-2-yl (W1) radical.

OH自由基和C ₄ H ₉的通道对异丁烯进行H吸收反应的动力学化学在当前工作中研究了通过将羟基加到异丁烯中而形成的O配合物。根据规范的过渡态理论，在考虑了隧穿效应的基础上，根据CCSD（T）/ CBS //的双能级量子化学方法构造势能面（PES），计算了它们在高压极限下的速率常数。 BHandHLYP / 6-311G（d，p）级别。文献中比较异丁烯的OH自由基与丙烯和3-己烯的OH吸收反应速率常数，发现差异小于6。讨论了羟基丁基彼此之间以及与异丁氧基的异构化途径详细。观察到，通过考虑隧穿效应，提高了H-吸收和经由H-转移的异构化的速率常数。随后，根据RRKM / ME理论计算了每个羟丁基自由基的多通道和异丁氧基自由基的主要通道的压力依赖性速率常数。在2-羟甲基-丙-2-基（W1）自由基的情况下，讨论了化学活化和热初始分布的影响。