Theoretical Studies of Reactive Intermediates and Kinetic Simplification

Rex Skodje获得了理论与计算化学项目的资助，致力于开发新的方法来提高对动态化学过程的理解。光谱量化技术将应用于过渡态动力学，将开发控制程序来优化初始状态，并将应用于气相光解离光谱和气体表面散射共振。将耦合非线性动力学方程的复杂系统简化为更简单的低维模型的方法也将得到发展。应用将包括燃烧化学、振动弛豫动力学和固体表面上adlayers的动力学。化学反应通常是间接进行的，即先形成不稳定的中间产物，然后再生成最终产物。这些中间物种往往不稳定，难以进行实验研究。因此，有必要采用量子力学模拟来表征这种系统的动力学特性。许多重要的问题，如大气化学和燃烧都是用非线性动力学方程来模拟的。新的算法可以简化这类方程的复杂网络。

Rex Skodje is supported by a grant from the Theoretical and Computational Chemistry Progam to develop new methods to improve the understanding of dynamical chemical processes. Spectral quantization techniques will be applied to transition state dynamics, control procedures will be developed to optimize initial states, and applications will be made to gas-phase photodissociation spectra and gas-surface scattering resonances. Methods for reducing complex systems of coupled nonlinear kinetic equations to simpler lower dimensional models will also be developed. Applications will include combustion chemistry, vibrational relaxation kinetics, and the kinetics of adlayers on solid surfaces. Chemical reactions often proceed indirectly, i.e., by first forming an unstable intermediate and then on to final products. These intermediate species are often unstable and difficult to study experimentally. Therefore it is necessary to employ quantum mechanical simulations to characterize the dynamics of such systems. Many important problems such as atmospheric chemistry and combustion are modeled using nonlinear kinetic equations. New algorithms will allow the simplification of complicated networks of such equations.