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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >A Systematic Theoretical Kinetics Analysis for the Waddington Mechanism in the Low-Temperature Oxidation of Butene and Butanol Isomers
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A Systematic Theoretical Kinetics Analysis for the Waddington Mechanism in the Low-Temperature Oxidation of Butene and Butanol Isomers

机译：丁烯和丁醇异构体低温氧化下瓦丁顿机理的系统理论动力学分析

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摘要

The Waddington mechanism, or the Waddington-type reaction pathway, is crucial for low-temperature oxidation of both alkenes and alcohols. In this study, the Waddington mechanism in the oxidation chemistry of butene and butanol isomers was systematically investigated. Fundamental quantum chemical calculations were conducted for the rate constants and thermodynamic properties of the reactions and species in this mechanism. Calculations were performed using two different ab initio solvers: Gaussian 09 and Orca 4.0.0, and two different kinetic solvers: PAPR and MultiWell, comprehensively. Temperature- and pressure-dependent rate constants were performed based on the transition state theory, associated with the Rice Ramsperger Kassel Marcus and master equation theories. Temperature-dependent thermochemistry (enthalpies of formation, entropy, and heat capacity) of all major species was also conducted, based on the statistical thermodynamics. Of the two types of reaction, dissociation reactions were significantly faster than isomerization reactions, while the rate constants of both reactions converged toward higher temperatures. In comparison, between two ab initio solvers, the barrier height difference among all isomerization and dissociation reactions was about 2 and 0.5 kcal/mol, respectively, resulting in less than 50%, and a factor of 2-10 differences for the predicted rate coefficients of the two reaction types, respectively. Comparing the two kinetic solvers, the rate constants of the isomerization reactions showed less than a 32% difference, while the rate of one dissociation reaction (P1 <-> WDT12) exhibited 1-2 orders of magnitude discrepancy. Compared with results from the literature, both reaction rate coefficients (R4 and R5 reaction systems) and species' thermochemistry (all closed shell molecules and open shell radicals R4 and R5) showed good agreement with the corresponding values obtained from the literature. All calculated results can be directly used for the chemical kinetic model development of butene and butanol isomer oxidation.
机译：Waddington机制或氟氯二顿型反应途径对于烯烃和醇的低温氧化至关重要。在这项研究中，系统地研究了丁烯和丁醇异构体的氧化化学中的Waddington机理。对该机制中反应和物种的速率常数和热力学性质进行了基本量子化学计算。使用两种不同的AB初始溶剂进行计算：高斯09和ORCA 4.0.0，以及两种不同的动力学求解器：PAPR和Multwell全面。基于过渡状态理论进行温度和压力依赖性速率常数，与稻米撞击器Kassel Marcus和主方程理论相关联。还在统计热力学基于统计热力学进行所有主要物种的温度依赖的热化学（形成，熵和热容量）。在两种类型的反应中，解离反应比异构化反应明显快，而两个反应的速率常数会聚在更高的温度下。相比，在两个AB初始溶剂之间，所有异构化和解离反应之间的阻挡高度差分别为约2和0.5kcal / mol，导致预测速率系数的2-10个差异为2-10倍分别两种反应类型。比较两种动力学溶剂，异构化反应的速率常数显示出小于32％的差异，而一种解离反应的速率（P1 - > WDT12）表现出1-2次差异差异。与文献结果相比，反应速率系数（R4和R5反应系统）和物种的热化学（所有闭合壳分子和开放壳体R4和R5）显示出与从文献中获得的相应值良好的一致性。所有计算结果都可直接用于丁烯和丁醇异构体氧化的化学动力学模型开发。

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