Theory of Chemical Reactions in Solution

詹姆斯·T·海恩斯教授得到了理论和计算化学项目的资助，继续他在溶液中化学反应理论的研究。他正在应用MD模拟、量子理论和分析理论的组合来获得关于溶剂化对化学反应速率的影响的见解。将寻求一些新的应用，包括：1)处理简单酸的电离，如盐酸和醋酸；2)涉及硝基烷烃和芳基硝基烷烃的质子转移；3)冰-空气界面上氯化氢的质子转移，以及空气-水界面上二氧化硫的质子转移，以此作为臭氧消耗和酸雨反应的模型。海因斯还将继续他的长期项目，涉及叔丁基氯在水溶液中的电离。解释气相化学反应行为的理论现在对小分子物种具有很强的预测性。虽然关于反应碰撞过程中发生的能量转移仍有许多工作在进行中，但反应碰撞过程中的大多数物理学都已被很好地理解。然而，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，到目前为止，最重要的溶剂是水。水溶液的存在对化学反应的影响还知之甚少。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。

Professor James T. Hynes is supported by a grant from the Theoretical and Computational Chemistry Program to continue his research in the theory of chemical reactions in solution. He is applying a combination of MD simulations, quantum theory, and analytical theory to obtain insights into the effects of solvation on the rates of chemical reactions. A number of new applications will be pursued including: 1) a treatment of the ionization of simple acids such as HCl and acetic acid; 2) proton transfers involving nitroalkanes and aryl nitroalkanes; 3) proton transfers for hydrogen chloride at the ice-air interface, and for sulfur dioxide at the air-water interface as a model for reactions involved in ozone depletion and acid rain. Hynes will also continue his longer term project involving the ionization of t-butyl chloride in aqueous solvent. Theories explaining the behavior of gas phase chemical reactions are now quite predictive for small molecular species. Although there is still much work in progress regarding energy transfer which occurs during the reactive collision process, most of the physics of the reactive encounter is well understood. However, by far the majority of reactions which are of interest to chemists take place in the solution phase, and by far the most important solvent is water. The effect which the presence of aqueous solvent has on a chemical reaction is much less well understood. Hynes is applying a combination of theory and computer simulations to determine the molecular nature of the solvent-solute interactions and their effects 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.