Probing the Chemistry of Reactive Molecules with Synchrotron Radiation

在这个项目中，我们将使用同步辐射（SR）在真空紫外和软x射线制度，以探测化学反应分子。这包括(a)单分子反应，如解离光离，(b)具有稳定分子的开壳物种的双分子反应，以及(c)导致迄今未探索的分子形成的反应。我们将关注燃烧、星际和大气化学中感兴趣的物质和反应，但也会关注无机化学中基本感兴趣的含硼分子。测量将在Paul Scherrer研究所（Villigen/CH）的存储环瑞士光源（SLS）和St. Aubin/Paris的同步加速器SOLEIL进行。这些实验将依赖于对离子和电子的探测。对于数据分析和解释，我们将继续与理论小组合作。除了热解，即热自由基生成，我们将采用SLS提供的新的光解流动反应器装置。它允许在双分子反应中产生不容易通过热过程获得的自由基，例如氧自由基。此外，该反应器允许研究自由基/分子反应动力学并确定反应速率。我们将从烯丙基，C3H5 + O2的反应开始，然后继续到其他碳氢化合物自由基和碳烯。我们也将扩大我们的研究计划到软x射线体制和探索核电子激发后的破碎动力学异氰酸，HNCO。这种分子包含有机分子的主要原子，并结合了小原子分子的优点和相当程度的复杂性。作为第一步，我们将记录HNCO的共振俄格光谱，并在下一步研究在各种共振激发下碎片化的位点选择性。反应性分子的VUV光电离和解离光电离将继续成为我们研究的重要组成部分。我们将确定反应分子的电离能和相关离解光电离通道的外观能AE0K。我们将重点关注具有杂原子的物质，例如吡啶的异构体C6H6N。此外，我们对BH3和B2Hx等含硼分子感兴趣。为了生成硼化合物，除了热解和光解源外，我们还将采用Soleil提供的放电流反应器。

In this project we will employ synchrotron radiation (SR) in the vacuum-ultraviolet and soft X-ray regime to probe the chemistry of reactive molecules. This includes (a) unimolecular reactions like dissociative photoionization, (b) bimolecular reactions of open-shell species with stable molecules, and (c) reactions that lead to the formation of hitherto unexplored molecules. We will focus on species and reactions that are of interest in combustion, interstellar and atmospheric chemistry, but also on boron-containing molecules of fundamental interest in inorganic chemistry. Measurements will be conducted at the storage rings Swiss Light Source (SLS) at the Paul Scherrer Institute (Villigen/CH) and the Synchrotron SOLEIL in St. Aubin/Paris. The experiments will rely on the detection of ions and electrons. For data analysis and interpretation we will continue to cooperate with theory groups.In addition to pyrolysis, i.e. thermal radical generation we will employ a new photolysis flow reactor setup available at the SLS. It permits to produce radicals in bimolecular reactions that are not easily accessible by thermal processes, for example oxyradicals. Furthermore this reactor permits to investigate the kinetics of radical/molecule reactions and to determine reaction rates. We will start with the reaction of allyl, C3H5 + O2 and then proceed to other hydrocarbon radicals and carbenes. We will also expand our research program to the soft X-ray regime and explore the fragmentation dynamics after excitation of core electrons in isocyanic acid, HNCO. This molecule contains the major atoms of organic molecules and combines the advantages of a small few-atom molecule with a considerable degree of complexity. As a first step we will record resonant Auger-spectra of HNCO and in the next step study the site-selectivity of fragmentation upon excitation of the various resonances. The VUV photoionization and dissociative photoionization of reactive molecules will continue to be an important part of our research. We will determine the ionization energies of reactive molecules and the appearance energies AE0K of relevant dissociative photoionization channels. We will focus on species with heteroatoms, for example the isomers of picolyl, C6H6N. Furthermore we are interested in boron-containing molecules like BH3 and B2Hx. For generating boron compounds, we will employ a discharge flow reactor available at Soleil in addition to pyrolysis and photolysis sources.