Theory of Chemical Reactions in Solution

在物理化学计划的这个项目中，海因斯将对溶液中几种重要类型的化学反应进行理论描述和数值计算。特别关注的是确定、理解和预测周围的液体溶剂如何改变这些反应的速度。将对电化学中重要的电子转移反应进行计算机模拟，以确定溶剂分子的运动在决定反应速率中所起的作用。对激光激发后发射的荧光辐射的相关模拟将进一步阐明这一作用。将对酸碱化学和催化中重要的质子转移反应进行理论和数值研究。这里的一个重要特征是确定量子力学隧穿在反应中所起的作用，以及这可能如何受到溶剂的影响。还将进行理论研究，以了解和预测溶液中离子解离反应的基本机理，以及与气相相比，溶剂如何显著改变反应行为。最后一组理论研究将确定溶剂如何充分改变高度振动激发的活性分子内的能量流动，以提高反应速度。

In this project in the Physical Chemistry Program, Hynes will formulate theoretical descriptions of and perform numerical calculations on several important types of chemical reactions in solution. The particular focus is on determining, understanding and predicting how the surrounding liquid solvent can alter the rates of these reactions. Computer simulations of electron transfer reactions, of the type important in electrochemistry, will be carried out to determine the role played by the motion of the solvent molecules in determining the reaction rates. Related simulations of fluorescent radiation emitted after laser excitation will further elucidate this role. Theoretical and numerical studies will be undertaken for proton transfer reactions of the type important in acid-base chemistry and catalysis. An important feature here is determination of the role played by quantum mechanical tunneling in the reactions and how this could be affected by the solvent. Theoretical studies will also be performed to understand and predict the fundamental mechanism of ionic dissociation reactions in solution and how the solvent can drastically alter the reaction behavior compared to the gas phase. A final set of theoretical studies will determine how a solvent might sufficiently alter the flow of energy inside a highly vibrationally excited and reactive molecule to enhance the rate of the reaction.