CAREER: Predictive Chemical Kinetics: Reaction Rate Estimation and Validation

William Green教授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、小胺和腈的部分氧化。过渡态理论和散射理论将允许先验地计算单个速率常数。所选常数将主要通过总反应速率测量和反应中间体的激光闪光光解进行实验验证。因此，群可加性、量子计算和有限实验数据的结合将用于估计未知的速率常数，包括它们的不确定性。已经实施的模拟算法将允许通过识别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的小有机分子的自由基化学。这在氧化和热解中最为重要，但也与材料合成（例如，等离子体增强CVD）和污染物的光修复有关。拨款的教育部分将包括开发一门新的研究生课程，强调分子模拟的预测化学动力学，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。预计这项拨款将对化工、燃料、环保行业以及工程教育产生影响。

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.