Spectroscopy and Reactivity of Organic Radicals

有机自由基将在气相中制备，并记录相应的红外吸收光谱。在另一组实验中，利用流动余辉装置，将研究气相中烃类自由基与负离子的反应性。要产生和研究的气相物种包括甲基、乙烯基、烯丙基、烯丙烯、苯基和苯基。自由基将通过带有高温喷嘴的热解超音速射流产生。将使用光电离质谱计跟踪氧化锆喷嘴顶部的热解流出物。在科罗拉多大学G.B.Ellison教授的指导下，来自有机动力学项目的这笔赠款支持对气相中的自由基和双自由基及其与各种物种的反应的研究。在许多化学转化过程中产生的一些最活跃的物种是含有一个未配对电子的自由基和包含两个未配对电子的双自由基。以前对有机自由基的研究大多涉及液体溶液中的反应，而埃里森教授将用高温喷嘴在气相中产生活性自由基物种。自由基将暴露在带电的气相分子流中，并直接观察到随后的化学变化。将实验结果与计算机模拟进行比较，将有助于更好地理解自由基和双自由基的反应。

Organic radicals will be prepared in the gas phase and the corresponding infrared absorption spectra recorded. In a separate set of experiments, utilizing a flowing afterglow apparatus, the reactivity of hydrocarbon radicals in the gas phase with negative ions will be investigated. Gas phase species to be generated and studied include methyl, vinyl, allyl, allene, phenyl, and benzyl radicals. The radicals will be produced via a pyrolysis supersonic jet with a high temperature nozzle. A photoionization mass spectrometer will be employed to follow the pyrolysis effluent at the head of a zirconia nozzle. %%% This grant from the Organic Dynamics Program supports an investigation of radicals and biradicals and their reactions with a variety of species in the gas phase under the direction of Professor G. B. Ellison at the University of Colorado. Some of the most reactive species produced during the course of many chemical transformations are radicals, which contain one unpaired electron, and biradicals, which contain two unpaired electrons. Whereas most of the previous work with organic radicals involved reactions in liquid solutions, Professor Ellison will generate reactive radical species in the gas phase with a high temperature nozzle. The radicals will be exposed to a stream of charged gas phase molecules and the chemical subsequent chemical transformations observed directly. Comparison of the experimental results with computer simulations will lead to a better understanding of the reactions of radicals and biradicals.