Rapid Reactions of Ions and Radicals in Organized and Constrained Media: Polymer Films and Zeolites

在有机动力学项目的支持下， 圣母大学研究离子和自由基的快速反应， 有组织和有约束力的媒体。 低能光化学和 有机探针分子的高能辐射分解反应 沸石和固体聚合物允许测定 产生的离子的光谱，允许探索的影响， 在这些系统中发生的独特离子动力学的主机修改。 在空腔内产生了小的有机溶剂池 沸石，约束和稳定通常是短寿命的 电荷分离的离子物种，否则将迅速 中和。 能量和电荷向探针分子的迁移 在固体聚合物主体内的聚合反应是由聚合物的激发引起的。 沸石和聚合物系统都具有共同的特征， 沉积在一个区域中的能量快速迁移到选定区域， 在目标部位产生化学反应 能源转换、运输和损失的基本问题在 许多重要技术过程的核心。 通过 光与高能电子反应的研究 有机分子被限制在一个严格限定的“笼子”内 托马斯教授没有在溶液中自由移动，而是探索了 自由电子、有机自由基的形成和反应机理 （含有奇数电子的化合物），以及有机离子 （带有正电荷或负电荷的化合物）。 正在进行的研究 针对“主机”的作用， 物种通过能量从宿主转移到有机体 分子包含在其中，并在运输的节制， 这些活性物质的反应性。 这些研究揭示了 能量激发过程例如在X射线中使用的那些 光刻，其中使用的高分辨率结构，例如， 在微电子电路生产中， 辐射引起的聚合物材料的形成或破坏

Supported by the Organic Dynamics Program, Professor Kerry Thomas of the University of Notre Dame studies rapid reactions of ions and radicals in organized and constrained media. Low-energy photochemical and high-energy radiolytic reactions of organic probe molecules held within zeolites and solid polymers permit assay of the rates of development of spectra of the resulting ions, allowing the exploration of the effects of host modification on the unique ion kinetics occurring in these systems. Small pools of organic solvents are created within the cavities of zeolites, constraining and stabilizing usually short-lived charge-separated ionic species which would otherwise be rapidly neutralized. Migration of energy and charge to probe molecules held within solid polymeric hosts is induced by excitation of the polymer. Both the zeolite and the polymer systems share a common feature, the rapid migration of energy deposited in one region to a selected region, creating chemistry at the targeted site. Fundamental questions of energy conversion, transport, and loss are at the heart of many important technological processes. Through an examination of the reactions with light and with high-energy electrons of organic molecules constrained to remain within a tightly-defined `cage` rather than freely moving in solution, Professor Thomas explores the mechanisms of formation and reaction of free electrons, organic radicals (compounds containing an odd number of electrons), and organic ions (compounds bearing either positive or negative charges). Ongoing studies target the role of the `host` both in the generation of these reactive species through the transfer of energy from the host to the organic molecules contained within it and in the moderation of the transport and reactivity of these reactive species. These studies shed light on energetic excitation processes such as those employed in x-ray photolithography, wherein high-resolution structures of use, for example, in microelectronic circuitry production, are produced through the radiation-induced formation or destruction of polymeric materials