Femtosecond Studies of Chemical Reaction Dynamics in Liquids

查尔斯·B·哈里斯，加州大学伯克利分校化学系，由化学部无机化学、生物无机化学和金属有机化学计划支持，利用飞秒UV泵浦/IR探针方法研究一类涉及C-H和Si-H键活化和卤素原子抽象的单电子和双电子过渡金属氧化加成反应的动力学和初始步骤。量子化学计算将用于辅助对观察到的反应中间体进行表征。一些关键的基元反应，即芳环滑移、金属介导的配体异构化、电子态分配和溶剂笼化，将被详细地研究。我们将详细研究溶剂分子的作用以及它们如何调节这些基本反应。实验结果将与模型系统上的分子动力学模拟相结合，以获得超快时间内基本步骤的微观图像。实验结果将导致对计算工具的测试和改进。将探索复杂化学反应背后的反应动力学。实验观察将与理论方法相结合，以掌握代表化学反应本质的键断裂和键形成。这项研究还将使人们更好地理解催化作用。学生和博士后助理将从他们与实验和理论企业的联系中成为一流的科学家。

Charles B. Harris, Department of Chemistry, University of California, Berkeley, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Chemistry Division to examine by femstosecond UV-pump / IR-probe methods the dynamics and the initial steps in an otherwise complex series of events for a class of one and two electron transition metal oxidative addition reactions involving C-H and Si-H bond activation and halogen atom abstraction. Quantum chemical calculation will be used to assist in the characterization of observed reaction intermediates. The dynamics of some critical elementary reactions, namely aromatic ring slippage, metal-mediated ligand isomerization, electronic state partitioning and solvent caging will be investigated in detail. The roles of solvent molecules and how they modulate these elementary reactions will be studied in detail. The experimental results will be combined with molecular dynamics simulations on model systems to obtain a microscopic picture of the elementary steps in ultrafast times. Experimental results will lead to tests and improvements of computational tools.Reaction dynamics underlying complex chemical reactions will be probed. Experimental observations will be coupled to theoretical methodologies to grasp bond breaking and bond making that represent the very essence of chemical reactions. The research will also lead to a better understanding of catalysis. Students and postdoctoral associates will become first-rate scientists from their association with both experimental and theoretical enterprises.