Femtosecond Studies of Chemical Reaction Dynamics in Liquids

液体中化学反应动力学的飞秒研究

• 批准号: 9970590
• 负责人: Charles Harris
• 金额: $ 66.25万
• 依托单位: University of California-Berkeley
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1999
• 资助国家: 美国
• 起止时间: 1999-04-01 至 2003-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9970590&HistoricalAwards=false
• 关键词: Femtosecond; Studies; Chemical; Reaction; Dynamics

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.

加州大学伯克利分校化学系的 Charles B. Harris 在化学系无机、生物无机和有机金属化学项目的支持下，通过飞秒紫外泵/红外探针方法检查了涉及 C-H 和 Si-H 键活化和卤素原子的一类和二电子过渡金属氧化加成反应的一系列复杂事件的动力学和初始步骤 抽象。量子化学计算将用于协助表征观察到的反应中间体。将详细研究一些关键基元反应的动力学，即芳环滑移、金属介导的配体异构化、电子态分配和溶剂封闭。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。实验结果将导致计算工具的测试和改进。将探讨复杂化学反应的反应动力学。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。该研究还将带来对催化作用的更好理解。学生和博士后将通过与实验和理论企业的联系成为一流的科学家。