Organic Ion-Molecule Chemistry

研究气相有机离子-分子反应的结构、反应活性和能量学之间的关系。一个可变温度流动余辉装置，连同从头算分子轨道计算，将用于进行这些研究。所得的信息将提供从浓缩阶段工作中无法获得的机制见解。要研究的种类包括乙烯基、环丙基和烷基阴离子。此外，还将研究单分子重排和取代基效应。这些研究将为一些重要领域提供关键信息，包括氢键、亲核取代、消去、轨道对称控制反应，以及结构、反应性和能量学之间的关系。许多重要的反应发生在气相，包括大气化学中涉及的大多数反应。因此，该项目不仅有助于理解控制各种化学转化的基本原理，而且还将为理解大气中发生的过程提供一个范例。在这项由有机动力学项目授予明尼苏达大学S. Kass教授的资助中，将特别关注气相中的反应和重排，这些反应和重排涉及带负电荷的有机物质阴离子。

The relationship between structure, reactivity, and energetics of gas phase organic ion-molecule reactions will be investigated. A variable temperature flowing afterglow apparatus, along with ab initio molecular orbital calculations, will be used to carry out these studies. The resulting information will provide mechanistic insights which are unavailable from condensed phase work. Species to be investigated include vinyl, cyclopropyl, and alkyl anions. As well, unimolecular rearrangements and substituent effects will be studied. These investigations will provide critical information on a number of important areas including hydrogen bonding, nucleophilic substitution, eliminations, orbital symmetry controlled reactions, and the relationship between structure, reactivity, and energetics. %%% Many important reactions occur are in the gas phase, including most of the reactions involved in atmospheric chemistry. This project will therefore not only contribute to an understanding of the fundamental principles which control a variety of chemical transformations, but will also provide a paridigm for understanding processes which occur in the atmosphere. In this grant from the Organic Dynamics Program to Professor S. Kass at the University of Minnesota, particular attention will be paid to investigation of reactions and rearrangements in the gas phase which involve negatively charged organic species called anions.