Theory of Chemical Reactions in Solution

在物理化学计划的这个项目中，海因斯将 制定理论描述并进行数值计算 几种重要化学反应的计算 在溶液中。 重点是确定， 了解和预测周围的液体溶剂 可以改变这些反应的速率。 电子转移反应的计算机模拟， 类型的重要电化学，将进行， 确定溶剂运动所起的作用 分子决定反应速率。 相关 激光后荧光辐射的模拟 激发将进一步阐明这种作用。 理论和 将对质子转移进行数值研究 酸碱化学中重要的反应类型， 催化作用 这里的一个重要特征是确定 量子力学隧道效应在反应中的作用 以及溶剂如何影响这一过程。 理论 还将进行研究，以了解和预测 离子解离反应的基本机理 溶液以及溶剂如何彻底改变反应 与气相相比。 最后一套理论 研究将确定溶剂如何能够充分改变 在一个高度振动激发的， 反应分子，以提高反应速率。

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.