Biradical-like Reactive Intermediates

9318469 Michl将探讨几个不同的研究领域。 双自由基类分子的单重态-三重态能隙将 由基体隔离电子能量损失决定 光谱（EELS）。通过键对自旋轨道耦合的贡献和自旋密度的机制 饱和自由基和双自由基中的离域化 分子轨道理论进行分析。新 全氟双自由基类物质将在 矩阵隔离的条件和一种新的方法， 将探索基质中的选择性反应。 的两个凯库勒结构之间的自动化 也将研究环丁二烯。结果 将为化学键提供新的理解， 活性中间体的性质，以及它们所起的作用 在热反应和光化学反应中。 %有机动力学计划的这一赠款支持 Josef Michl教授继续研究 科罗拉多大学。通常情况下，总共有四个 其他原子和与碳有关的电子对。 碳自由基通常是反应性中间体， 总共有三个其他原子和电子对 加上一个额外的电子。含有一个和两个电子的物质 将通过复杂的光谱技术研究自由基位点， 低温下的方法。两者之间的相互作用 激进的网站将被处理。的计算 这些物种的结构和能量将被执行， 以补充实验结果。这些结果 将提供对键合和性质的新理解 反应性中间体，以及它们在热和 光引发的反应。 ***

9318469 Michl Several different areas of research will be explored. Singlet-triplet energy gaps of biradical-like molecules will be determined by matrix-isolation electron energy loss spectroscopy (EELS). Through bond contributions to spin- orbit coupling and the mechanisms of spin density delocalization in saturated radicals and biradicals using molecular orbital theory will be analyzed. New perfluorinated biradical-like species will be prepared under conditions of matrix-isolation and a new approach to selective reactions in matrices will be explored. Automerization between the two Kekule structures of cyclobutadiene will be investigated as well. The results will provide new understanding of the chemical bonding and properties of reactive intermediates, and the role they play in thermal and photochemical reactions. %%% This grant from the Organic Dynamics Program supports the continuing research of Professor Josef Michl at the University of Colorado. Normally, there are a total of four other atoms and pairs of electrons associated with carbon. Carbon radicals are typically reactive intermediates and have a total of three other atoms and pairs of electrons plus one additional electron. Species containing one and two radical sites will be studied by sophisticated spectroscopic methods at low temperatures. Interactions between the two radical sites will be addressed. Calculations of the structure and energy of these species will be carried out as well to complement the experimental results. These results will provide a new understanding of bonding and properties of reactive intermediates, and their role in thermal and photo-initiated reactions. ***