Theoretical Studies of Organic Reactions in Solution

威廉·乔根森教授得到了 理论和计算化学课程执行 有机化学反应的理论研究， 气相和溶液中使用量子化学的组合， 力学、统计力学和分子动力学 模拟 本理论研究的结果提供了 一个重要的解释化学反应在 基本分子水平的理解。 Jorgensen采用从头算分子轨道计算， 为气相中的反应提供能量表面， 描述溶质-溶剂相互作用的势函数。 溶剂化的效果然后通过计算 溶液中的自由能表面。 这涉及到蒙特卡洛或 反应体系的分子动力学模拟 大约300个溶剂分子在一个周期性的细胞中。 最后 反应动力学通过轨迹计算来研究， 都是从过渡状态区域开始的。 这些 计算提供了关键问题的详细信息 包括气相中的反应机理和 溶液，中间体的存在，溶剂的来源 诱导活化势垒，溶剂化沿着 反应路径，反应过程中的能量再分配， 溶剂在确定反应动力学中的动态作用。

Professor William Jorgensen is supported by a grant from the Theoretical and Computational Chemistry Program to perform theoretical studies of organic chemical reactions both in the gas phase and in solution using a combination of quantum mechanics, statistical mechanics and molecular dynamics simulations. The results of this theoretical research provide an important interpretation of chemical reactivity at the fundamental molecular level of understanding. Jorgensen employs ab initio molecular orbital calculations to provide energy surfaces for reactions in the gas phase and potential functions that describe solute-solvent interactions. The effect of solvation is then determined by computing the free energy surfaces in solution. This involves Monte Carlo or molecular dynamics simulations for the reacting systems plus about 300 solvent molecules in a periodic cell. Finally, the reaction dynamics are studied by trajectory calculations that are started in the transition state regions. These computations provide detailed information on key issues including the reaction mechanisms in the gas phase and in solution, the existence of intermediates, the origin of solvent induced activation barriers, changes in solvation along reaction paths, energy redistribution during reactions, and the dynamic role of the solvent in determining reaction kinetics.