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O(3P)+1,2-丁二烯反应的交叉分子束和理论研究:丙烯+CO和亚乙基+乙烯酮反应的主要分子通道
Adriana Caracciolo,Gianmarco Vanuzzo,Nadia Balucani,Domenico Stranges,Silvia Tanteri,Carlo Cavallotti,Piergiorgio Casavecchia*
作者单位E-mail
Adriana Caracciolo 意大利佩鲁贾大学化学 生物 生物技术系佩鲁贾 06123  
Gianmarco Vanuzzo 意大利佩鲁贾大学化学 生物 生物技术系佩鲁贾 06123  
Nadia Balucani 意大利佩鲁贾大学化学 生物 生物技术系佩鲁贾 06123  
Domenico Stranges 意大利La Sapienza大学化学系罗马 00185  
Silvia Tanteri 意大利La Sapienza大学化学系罗马 00185  
Carlo Cavallotti 意大利米兰理工学院材料与化学工程系米兰 20131  
Piergiorgio Casavecchia* 意大利佩鲁贾大学化学 生物 生物技术系佩鲁贾 06123 piergiorgio.casavecchia@unipg.it 
摘要:
详细了解O(3P)与不饱和烃的多通道燃烧反应机理需要鉴定所有主要反应产物、确定分支比、评估三重态与单重态势能面之间的系间窜跃. 将交叉分子束实验、软电离、质谱、飞行时间分析,以及高级从头算计算三重态/单线态势能面,RRKM/Master方程计算支化比包括系间窜跃,均可以获得最佳效果. 最近已经证明这些方法对于含有两个或三个碳原子的最简单的不饱和烃(炔烃,烯烃,二烯)和O(3P)反应是成功的. 本文通过交叉分子束与理论相结合的方法研究O(3P))和含有四个C原子的二烯类化合物, 1,2-丁二烯(甲基芳烃)的反应,探索产物分布、分支比和系间窜跃如何随着分子复杂性的增加而变化, 即从O(3P)和丙二烯反应到O(3P)1,2-丁二烯的反应变化. 尤其关注了最重要的导致链终止的主导分子通道(即形成丙烯+CO(分支≥0.5) 和亚乙基+乙烯酮(分支比≥0.15))与导致链传递的自由基形成通道进行对比(分支比≥0.35).
关键词:  反应散射,交叉分子束,O(3P)反应动力学,O(3P)+二烯反应,软电子电离,系间跨越,从头算量子化学
DOI:10.1063/1674-0068/cjcp1812281
分类号:
基金项目:
Crossed Molecular Beams and Theoretical Studies of the O(3P)+1,2-Butadiene Reaction: Dominant Formation of Propene+CO and Ethylidene+Ketene Molecular Channels
Adriana Caracciolo,Gianmarco Vanuzzo,Nadia Balucani,Domenico Stranges,Silvia Tanteri,Carlo Cavallotti,Piergiorgio Casavecchia*
Abstract:
Detailed understanding of the mechanism of the combustion relevant multichannel reactions of O(3P) with unsaturated hydrocarbons (UHs) requires the identification of all primary reaction products, the determination of their branching ratios and assessment of intersystem crossing (ISC) between triplet and singlet potential energy surfaces (PESs). This can be best achieved combining crossed-molecular-beam (CMB) experiments with universal, soft ionization, mass-spectrometric detection and time-of-flight analysis to high-level ab initio electronic structure calculations of triplet/singlet PESs and RRKM/Master Equation computations of branching ratios (BRs) including ISC. This approach has been recently demonstrated to be successful for O(3P) reactions with the simplest UHs (alkynes, alkenes, dienes) containing two or three carbon atoms. Here, we extend the combined CMB/theoretical approach to the next member in the diene series containing four C atoms, namely 1,2-butadiene (methylallene) to explore how product distributions, branching ratios and ISC vary with increasing molecular complexity going from O(3P))+propadiene to O(3P)+1,2-butadiene. In particular, we focus on the most important, dominant molecular channels, those forming propene+CO (with branching ratio ∽0.5) and ethylidene+ketene (with branching ratio ∽0.15), that lead to chain termination, to be contrasted to radical forming channels (branching ratio ∽0.35) which lead to chain propagation in combustion systems.
Key words:  Reactive scattering, Crossed molecular beams, O(3P) reaction dynamics, O(3P)+diene reactions, Soft electron ionization, Intersystem crossing, Ab initio quantum chemistry