Spectroscopy and Dynamics of Ions

Lineberger已经提交了一份更新提案， 气相中负离子及其团簇的研究 光电子能谱和离子的超快泵浦-探测激发 配合物 通过这些技术，结构信息和 反应动力学将被调查的一个广泛的系统， 是化学瞬变、活性中间体或过渡 国家物种。 要研究的分子中有有机自由基 和双自由基，金属和金属簇，以及两者的过渡态 单分子和双分子过程。 电子亲合能， 单重态-三重态分裂、振动频率和几何 将获得信息。 苯炔的邻、Meta、帕拉形式 （C6 H4）将使用立体化学控制合成。 单分子 超快方法研究的过程包括1，2氢 亚乙烯基转移形成乙炔。 离子在溶剂中的动力学 笼子也将扩大以下产品的外观 笼式解体以及电子后的溶剂重组 以部分溶剂化的离子转移。 这些研究的一个目标是 增加对推动发展的过程的定量了解， 最简单的化学变化 通过研究这种化学物质 分子的转变，既孤立， 在溶剂物质的包围下，Lineberger将能够证明 不同溶剂对反应性和反应速率的影响 这些反应进行的时间。

Lineberger has submitted a renewal proposal to investigate the properties of negative ions and their clusters in the gas phase using negative ion photoelectron spectroscopy and ultrafast pump-probe excitation of ionic complexes. With these techniques both the structural information and the reaction dynamics will be investigated for a broad class of systems which are either chemical transients, reactive intermediates, or transition state species. Among the molecules to be studied are organic radicals and biradicals, metals and metal clusters, and transition states for both unimolecular and bimolecular processes. Electron affinities, singlet-triplet splittings, vibrational frequencies, and geometrical information will be obtained. Ortho, meta, and para forms of benzyne (C6H4) will be synthesized using stereochemical control. Unimolecular processes investigated by ultrafast methods include the 1,2 hydrogen shift in vinylidene to form acetylene. The dynamics of ions in a solvent cage will also be extended by following the appearance of products of cage disintegration as well as solvent reorganization following electron transfer in partially solvated ions. One goal of these studies is to increase the quantitative understanding of the processes driving the simplest chemical transformations. By studying the chemical transformations of molecules which are both isolated as well as surrounded by solvent species, Lineberger will be able to demonstrate the effect that different solvents have on reactivity as well as on the rates at which these reactions proceed.