Ultrafast Kinetic Studies of Molecular Rearrangements

有了这个更新的奖项，有机和大分子化学项目将继续支持科罗拉多大学博尔德分校化学系凯文·s·彼得斯教授的工作。该研究将扩展PI的研究，使用飞秒、皮秒和纳秒瞬态吸收光谱来研究化学反应的实时动力学。研究的体系包括碳阳离子中1,2和1,3氢化物和氘化物的移位，碳阳离子中1,2烷基的移位，以及各种取代二苯甲酮/N，N-二烯丙苯胺自由基离子对中质子/氘核转移的动力学。这些动力学研究的结果将在绝热和非绝热重排的背景下进行分析，以评估过渡态理论描述凝聚相中电荷位移反应动力学的有效性。这些质子和氢化物转移动力学的研究有望为有机化学、物理化学和生物化学中这类反应的理论和实验处理提供重要的基础信息。

With this renewal award, the Organic and Macromolecular Chemistry Program continues its support of the work of Professor Kevin S. Peters of the Department of Chemistry at the University of Colorado, Boulder, CO. The research will extend the PI's research using femtosecond, picosecond, and nanosecond transient absorption spectroscopy to study the real time dynamics of chemical reactions. Systems to be investigated include 1,2 and 1,3 hydride and deuteride shifts in carbocations, 1,2 alkyl shifts in carbocations, and the dynamics of proton/deuteron transfer in a variety of substituted benzophenones/N,N-diallylaniline radical ion pairs. The results of these kinetic studies will be analyzed within the context of adiabatic and non-adiabatic rearrangements in order to assess the validity of transition state theory for describing the dynamics of charge displacement reactions in the condensed phase.These studies of the dynamics of proton and hydride transfer are expected provide important fundamental information that will impact on theoretical and experimental treatments of such reactions in organic, physical, and biological chemistry.