Hydrogen Abstraction Radical Reactions: Entrance Channel Control

艾略特教授科罗拉多州立大学的伯恩斯坦得到了实验物理化学计划的支持，对小自由基及其在气相中的反应进行实验和理论研究。 基本问题涉及到双分子反应的详细描述。 为了达到所需的细节水平，需要减少反应坐标的维数，PI提出了一种实验方法。 小的自由基，如NCO和NO3将与含氢的共反应物在光束中络合，并且反应是光引发的。 随后的氢提取产品进行分析，使用激光诱导荧光或质量分辨激发光谱。 采用从头算方法在反应物络合物激发态势能面上跟踪反应，寻找生成产物自由基的路径。除了推进有关双分子反应的基础知识外，这项研究还将有助于更全面地了解这种络合物和激发电子态在大气和燃烧化学中所起的作用。

Professor Elliot R. Bernstein of Colorado State University is supported by the Experimental Physical Chemistry program to perform experimental and theoretical studies on small radicals and their reactions in the gas phase. The fundamental question pertains to the detailed description of bimolecular reactions. In order to achieve the desired level of detail, it is required that the dimensionality of the reactive coordinates be reduced, and the PI proposes an experimental means to do so. Small radicals such as NCO and NO3 will be complexed with hydrogen-containing coreactant species in a beam, and the reaction is photoinitiated. The ensuing hydrogen abstraction products are analyzed using laser induced fluorescence or mass-resolved excitation spectroscopy. Ab initio theory will be employed to follow the reaction on the reactant complex excited electronic state potential energy surface to find the path for the generation of the product radical. In addition to advancing fundamental knowledge about bimolecular reactions, this research will contribute to a fuller understanding of the role played by such complexes and excited electronic states in atmospheric and combustion chemistry.