Crossed molecular beam studies of bimolecular reactions of atomic oxygen with nitrogen-bearing organic molecules (nitriles and N-heterocyclic)

IF 2.1 4区 综合性期刊 Q2 MULTIDISCIPLINARY SCIENCES Rendiconti Lincei-Scienze Fisiche E Naturali Pub Date : 2024-02-06 DOI:10.1007/s12210-023-01217-6
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Abstract

In this contribution, dedicated to the memory of Prof. Gian Gualberto Volpi, we provide a short review of recent work carried out in our laboratory on reactive scattering studies of the reaction dynamics of atomic oxygen with nitrogen-bearing organic molecules. Specifically, we focus on the polyatomic bimolecular reactions of atomic oxygen, both in the ground and first excited state, O(3P) and O(1D), with the simplest unsaturated nitriles, namely HCCCN (cyanoacetylene) and CH2CHCN (cyanoethylene, or acrylonitrile), and with the simplest six-member ring N-heterocyclic compound, pyridine (C5H5N). Using the crossed molecular beam (CMB) scattering technique with universal electron-impact ionization mass-spectrometric detection and time-of-flight analysis to measure product angular and velocity distributions, the primary product channels and their branching fractions were determined, thus assessing the central role played by intersystem-crossing (ISC) in this class of reactions. The experimental work was synergistically accompanied by theoretical calculations of the relevant triplet and singlet potential energy surfaces (PESs) to assist the interpretation of experimental results and elucidate the reaction mechanism, including extent of ISC. Cyanoacetylene and cyanoethylene are of considerable interest in astrochemistry being ubiquitous (and relatively abundant) in space including comets and the upper atmosphere of Titan. Being oxygen the third most abundant element in space, the title reactions are of considerable relevance in the chemistry of extraterrestrial environments. In addition, they are also important in combustion chemistry, because thermal decomposition of pyrrolic and pyridinic structures present in bound N-containing fuels generates N-bearing compounds including, in particular, the above two nitriles.

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原子氧与含氮有机分子(腈类和 N-杂环)的双分子反应的交叉分子束研究
摘要 在这篇献给 Gian Gualberto Volpi 教授的文章中,我们简要回顾了我们实验室最近在原子氧与含氮有机分子反应动力学的反应散射研究方面开展的工作。具体来说,我们重点研究了原子氧在基态和第一激发态(O(3P)和 O(1D))与最简单的不饱和腈类(即 HCCCN(氰乙炔)和 CH2CHCN(氰乙烯或丙烯腈))以及最简单的六元环 N-杂环化合物吡啶(C5H5N)的多原子双分子反应。利用交叉分子束(CMB)散射技术和通用电子撞击电离质谱检测及飞行时间分析来测量产物的角度和速度分布,确定了主要产物通道及其支化分数,从而评估了系统间交叉(ISC)在这类反应中所起的核心作用。实验工作与相关三重态和单重态势能面(PES)的理论计算协同进行,以帮助解释实验结果和阐明反应机理,包括 ISC 的程度。氰乙炔和氰乙烯在太空(包括彗星和土卫六上层大气)中无处不在(且相对丰富),因此在天体化学中具有相当重要的意义。氧是太空中含量第三高的元素,因此这两个反应在地外环境化学中具有重要意义。此外,它们在燃烧化学中也很重要,因为存在于结合含氮燃料中的吡咯和吡啶结构热分解会产生含氮化合物,特别是包括上述两种腈。
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来源期刊
Rendiconti Lincei-Scienze Fisiche E Naturali
Rendiconti Lincei-Scienze Fisiche E Naturali MULTIDISCIPLINARY SCIENCES-
CiteScore
4.10
自引率
10.00%
发文量
70
审稿时长
>12 weeks
期刊介绍: Rendiconti is the interdisciplinary scientific journal of the Accademia dei Lincei, the Italian National Academy, situated in Rome, which publishes original articles in the fi elds of geosciences, envi ronmental sciences, and biological and biomedi cal sciences. Particular interest is accorded to papers dealing with modern trends in the natural sciences, with interdisciplinary relationships and with the roots and historical development of these disciplines.
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