Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association,Physical Chemistry Chemical Physics

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Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2020/03/09 , DOI: 10.1039/d0cp00306a
Alexander N. Morozov _{1,

2,

3,

4} , Alexander M. Mebel _{1,

2,

3,

4}

Affiliation

Potential energy surface for the phenyl + propargyl radical recombination reaction has been studied at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G** level of theory for the closed-shell singlet species and at the triplet–singlet gap CASPT2/cc-pVTZ-CCSD(T)-F12/cc-pVTZ-f12//CASSCF/cc-pVTZ level of theory for the diradical species. High-pressure limit rate constants for the barrierless channels were evaluated with variable reaction coordinate transition state theory (VRC-TST). Rice–Ramsperger–Kassel–Marcus Master Equation (RRKM-ME) calculations have been performed to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. The entrance channels of the radical association reaction produce 3-phenyl-1-propyne and phenylallene which can further dissociate/isomerize into a variety of unimolecular and bimolecular products. Theoretical evidence is presented that, at combustion relevant conditions, the phenyl + propargyl recombination provides a feasible mechanism for the addition of a second five-member ring to the first six-member aromatic ring producing the prototype two-ring species indene and indenyl. Rate expressions for all important reaction channels in a broad range of temperatures and pressures have been generated for kinetic modeling.

中文翻译：

苯基+炔丙基缔合反应机理和动力学的理论研究

在CCSD（T）-F12 / cc-pVTZ-f12 // B3LYP / 6-311G **的理论水平上研究了苯基+炔丙基自由基重组反应的势能面。三重态-单缝隙CASPT2 / cc-pVTZ-CCSD（T）-F12 / cc-pVTZ-f12 // CASSCF / cc-pVTZ对于双基物种的理论水平。使用可变反应坐标过渡态理论（VRC-TST）评估了无障碍通道的高压极限速率常数。赖斯-拉姆斯伯格-卡塞尔-马库斯主方程（RRKM-ME）的计算已经进行，以评估温度和压力相关的现象学速率常数和产物分支比。自由基缔合反应的入口通道产生3-苯基-1-丙炔和苯丙二烯，它们可以进一步离解/异构化成各种单分子和双分子产物。提出了理论证据，在燃烧相关条件下，苯基+炔丙基重组为将第二个五元环加到第一个六元芳环上提供了可行的机制，从而产生了原型二环物种茚和茚基。已经为动力学建模生成了在宽范围的温度和压力下所有重要反应通道的速率表达式。苯基+炔丙基重组为将第二个五元环加到第一个六元芳环上提供了可行的机制，从而产生了原型二环物种茚和茚基。已经为动力学建模生成了在宽范围的温度和压力下所有重要反应通道的速率表达式。苯基+炔丙基重组为将第二个五元环加到第一个六元芳环上提供了可行的机制，从而产生了原型二环物种茚和茚基。已经为动力学建模生成了在宽范围的温度和压力下所有重要反应通道的速率表达式。

更新日期：2020-04-06

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