Generation and Chemistry of Biradicals and High Energy Molecules

有机动力学项目的这笔赠款支持内华达大学雷诺分校罗伯特·S·谢里丹教授指导的研究项目。我们将研究双自由基在基质和溶液中的光化学生成。将研究偶氮前体分解为间光加成双自由基的机理，以确定决定反应表面分步分配和协同分配的结构特征。将进行旨在确定热分子反应在基质和溶液中是否重要的实验。还将探索二脱氢芳香双自由基光化学途径。将研究光与低温下捕获在固体基质中的高能分子之间的相互作用。低温基质通过有效地将这些活性中间体彼此隔离，从而延长在这些光化学反应中形成的活性物种的寿命。添加比形成这些活性中间体所需的能量更多的能量的效果将被仔细研究。这些研究将为高能分子和中间体的分解途径提供重要信息。

This grant from the Organic Dynamics Program supports the research program directed by Professor Robert S. Sheridan at the University of Nevada Reno. Photochemical generation of biradicals in matrices and in solution will be examined. The mechanism of decomposition of the azo precursors to meta-photoaddition biradicals will be studied in order to determine the structural features which dictate stepwise versus concerted partitioning on the reaction surface. Experiments designed to determine if hot molecule reactions are important in matrices and in solution will be conducted. Photochemical pathways to didehydroaromatic biradicals will also be explored. %%% The interaction of light with highly energetic molecules trapped at low temperature in solid matrices will be examined. The low temperature matrix will prolong the lifetime of reactive species formed in these photochemical reactions by effectively isolating these reactive intermediates from each other. The effect of adding more energy than necessary to form these reactive intermediates will be carefully examined. These studies will provide important information on the decomposition pathways of highly energetic molecules and intermediates.