Theory of Chemical Reactions in Solution, in Clusters, and at Surfaces

科罗拉多大学化学系的James Hynes受化学系物理化学项目资助，研究溶液、小簇和表面原型反应的动力学理论。将为实验提供定量预测和定性解释。计算将使用量子电子结构方法、分子动力学、分析理论和模型进行。溶液相的研究将集中在两个方面：(1)激发光子转移反应（ESPT），在该反应中，光激发使酸度急剧增加。(2)电解质中的反应动力学。研究了氯化叔丁酯在盐溶液中SN1电离原型单分子反应动力学。此外，还将研究引起上层大气臭氧耗竭的非均相表面化学反应。到目前为止，化学家们感兴趣的大多数反应都是在溶液中进行的，而最重要的溶剂是水。含水溶剂的存在对化学反应的影响尚不完全清楚。海因斯正在运用理论和计算机模拟相结合的方法来确定溶剂-溶质相互作用的分子性质及其对溶液中化学反应速率的影响。他还将这些理论方法应用于酸雨和臭氧消耗等重要环境问题的研究。

James Hynes of the Chemistry Department of the University of Colorado is funded by the Physical Chemistry Program of the Chemistry Division to study the kinetic theory of prototype reactions in solutions, small clusters and at surfaces. Quantitative predictions and qualitative interpretations will be provided for experiments. The calculations will be carried out using quantum electronic structure methods, molecular dynamics, analytic theories and models. The solution phase research will focus in two areas: (1) Excited photon transfer reactions (ESPT) in which acidity is dramatically increased by photoexcitation. (2) Reaction dynamics in electrolytes. The dynamics of prototype unimolecular SN1 ionization reaction of tertiary butyl chloride in salt solutions will be studied. Furthermore, heterogeneous surface chemical reactions responsible for the depletion of the ozone in the upper atmosphere will be investigated. By far the majority of reactions which are of interest to chemists take place in the solution phase, and the most important solvent is water. The effect which the presence of aqueous solvent has on a chemical reaction is still not fully understood. Hynes is applying a combination of theory and computer simulations to determine the molecular nature of solvent-solute interactions and their effect on the rates of chemical reactions in solution. He is also applying these theoretical methods to studies of important environmental problems such as acid rain and ozone depletion.