The thermodynamic and kinetic investigation for the reaction of ethylperoxy radical (CH₃CH₂OO^•) with ethanol (CH₃CH₂OH) was studied computationally with variational transition state theory. The geometry optimization calculations showed that both the reactants have two conformers. The energetics and thermodynamic properties were calculated using the G4 composite method. The results showed that the abstraction of H atom from the ─CH₂─ site is most feasible, when compared to the other pathways, since it has the lowest energy barrier. The rate coefficient calculations for the title reaction were carried out using the multistructural canonical variational transition state theory with small curvature tunneling corrections in the temperature range of 400‐1500 K. The results showed a similar trend to that of the energetics in which the abstraction of the H atom from the ─CH₂─ site has a larger rate coefficient, when compared to other reaction pathways. The reactivity trend towards the H atom abstraction by ethylperoxy radicals varies as ─CH₂ > ─CH₃ > ─OH. The contributions from the ground‐state conformers of both the reactants were included into the total kinetics using the Boltzmann probability distribution. The obtained temperature‐dependent expression for the studied reaction is k_total = 1.51 × 10⁻³² T^6.3 exp(−3691/T) cm³ molecule⁻¹ s⁻¹.

中文翻译：

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乙基过氧自由基与乙醇反应的动力学研究

用变分过渡态理论对乙基过氧自由基（CH ₃ CH ₂ OO ^•）与乙醇（CH ₃ CH ₂ OH）的反应进行了热力学和动力学研究。几何优化计算表明两种反应物均具有两个构象异构体。使用G4复合方法计算能量和热力学性质。结果表明，H原子是从CH ₂原子中提取出来的。－与其他途径相比，场地是最可行的，因为它的能垒最低。标题反应的速率系数计算是使用多结构典型变分过渡态理论在400〜1500 K的温度范围内进行小曲率隧道校正的结果。与其他反应途径相比，来自CH ₂部位的H原子具有较大的速率系数。乙基过氧自由基对H原子的反应性趋势随─CH ₂ >─CH ₃而变化>─OH。两种反应物的基态构象异构体的贡献均使用玻耳兹曼概率分布计入总动力学。所研究反应的温度依赖性表达式为k _total  = 1.51×10 ^-32 T ^6.3 exp（-3691 / T）cm ³分子^-1 s ^-1。