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

科罗拉多大学化学系的詹姆斯·海恩斯是由化学系物理化学计划资助的，研究溶液、小团簇和表面上的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，光激发大大增加了酸性。(2)电解液中的反应动力学。研究了叔丁基氯化物在盐溶液中单分子SN1电离反应的动力学。此外，还将调查造成高层大气中臭氧消耗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发生在溶液相中，而最重要的溶剂是水。水溶液的存在对化学反应的影响仍未完全了解。海因斯正在应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度的影响。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.