CAREER: Predictive Chemical Kinetics: Reaction Rate Estimation and Validation

职业：预测化学动力学：反应速率估计和验证

• 批准号: 9875335
• 负责人: William Green
• 金额: $ 20万
• 依托单位: Massachusetts Institute of Technology
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1999
• 资助国家: 美国
• 起止时间: 1999-06-01 至 2003-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9875335&HistoricalAwards=false
• 关键词: CAREER; Predictive; Chemical; Kinetics; Reaction

Professor William Green will develop algorithmic and molecular modeling methodology to predict the kinetics of complex reaction systems such as combustion of fuels and partial oxidation of hydrocarbons and small amines and nitriles. Transition state theory and scattering theory will allow a priori calculation of individual rate constants. Selected constants will be experimentally validated primarily by overall reaction rate measurement and laser flash photolysis of reactive intermediates. Thus a combination of group additivity, quantum calculations and limited experimental data will be used to estimate unknown rate constants, including their uncertainty. A simulation algorithm --already implemented-- will allow the construction of complex reaction schemes by identifying the kinetically significant species. The focus will be on the free-radical chemistry of small organic molecules in the gas phase and in weakly interacting solvents. Such is most important in oxidation and pyrolysis, but is also relevant to materials synthesis (e.g., plasma-enhanced CVD) and photo-remediation of pollutants. The educational portion of the grant will entail the development of a new graduate course in predictive chemical kinetics emphasizing molecular simulation, as well as modules for the existing undergraduate courses at MIT. Dissemination will be done via a web-site. The impact of this grant is expected to occur in the chemical, fuel, and environmental protection industries, as well as in engineering education.

教授威廉绿色将开发算法和分子建模方法来预测复杂反应系统的动力学，如燃料的燃烧和碳氢化合物和小胺和腈的部分氧化。过渡态理论和散射理论将允许个别速率常数的先验计算。选定的常数将主要通过整体反应速率测量和活性中间体的激光闪光光解进行实验验证。因此，结合基团加和性，量子计算和有限的实验数据将被用来估计未知的速率常数，包括其不确定性。一种模拟算法-已经实施-将允许通过确定动力学上重要的物种来构建复杂的反应方案。 重点将放在气相和弱相互作用溶剂中有机小分子的自由基化学。这在氧化和热解中是最重要的，但也与材料合成有关（例如，等离子体增强CVD）和污染物的光修复。赠款的教育部分将需要开发一门新的预测化学动力学研究生课程，强调分子模拟，以及麻省理工学院现有本科课程的模块。将通过一个网站进行传播。这项赠款的影响预计将发生在化学，燃料和环境保护行业，以及工程教育。