Kinetic and Thermodynamic Studies of Long Distance Electron Transfer Reactions

长距离电子转移反应的动力学和热力学研究

• 批准号: 9206765
• 负责人: Matthew Zimmt
• 金额: $ 42.2万
• 依托单位: Brown University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1992
• 资助国家: 美国
• 起止时间: 1992-07-01 至 1997-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9206765&HistoricalAwards=false
• 关键词: Kinetic; Thermodynamic; Studies; Long; Distance

An investigation of the factors which govern the rate and efficiency of electron transfer reactions will be conducted. The effect of spacers separating donor and acceptor groups will be evaluated by measuring photoinduced charge separation rate constants and emission spectra as a function of temperature and calculating free energies of electron transfer. Picosecond photocalorimetry will be used to evaluate enthalpy and volume changes which occur upon electron transfer. Finally, through-solvent electron coupling and its impact upon electron transfer will be investigated in structurally rigid molecules. Correlations between transfer rate constants, electronic coupling matrix elements, and solvent band structure will be analyzed. %%% A process which is common to a large number of chemical reactions is the rapid transfer of electrons. With this grant from the Organic Dynamics Program, Profssor Matthew Zimmt of Brown University will investigate the factors which govern the rate of electron transfer processes which are complete within a few trillionths of a second. The parameters which influence electron transfer will be investigated using molecules specially designed so that both the distance between donor and acceptor groups and the identity and positions of the intervening atoms are well-defined. The results of the study may make it possible to design molecular systems which will maximize electron transfer efficiency.

对影响失业率的因素进行了调查， 将进行电子转移反应的效率。 分隔供体和受体基团的间隔物的作用将 通过测量光致电荷分离率来评价 常数和发射光谱作为温度的函数， 计算电子转移的自由能。皮秒 将使用光量热法来评估焓和体积 电子转移时发生的变化。最后， 通过溶剂的电子耦合及其对电子的影响 将在结构刚性分子中研究转移。 电子转移速率常数之间的相关性 耦合矩阵元素，溶剂带结构将是 分析了 %%% 一个过程，这是常见的大量化学品 反应的关键是电子的快速转移。有了这笔补助金 来自有机动力学项目的Matthew Zimmt教授， 布朗大学将调查影响 电子转移过程的速率，在一个 万亿分之几秒影响的参数 电子转移将使用分子进行研究 特别设计，使供体和 受体基团以及受体基团的身份和位置。 介入原子是明确定义的。研究结果 也许可以设计出分子系统， 最大化电子转移效率。