Experimental and Theoretical Investigations of Organic Reaction Rates and Mechanisms

将对各种基本化学反应的基本机制进行研究，从周环过程到卡宾和单线态氧的反应。将获得实验结果，并与前线分子轨道和从头计算进行适当的比较。对于周环反应，将注意取代基的影响。实验的同位素效应将与理论计算得出的预测进行比较。禁戒周环反应的分子动力学将用可变过渡态理论进行研究，并将进行从头计算来生成势能面。我们将用统计力学和过渡态理论研究卡宾和单重态氧反应的动力学。来自有机动力学项目的这笔赠款支持加州大学洛杉矶分校肯德尔·N·胡克教授的继续工作。这些研究的目的是为了更好地了解一些重要的化学反应。该研究项目的很大一部分将利用高速计算机来预测反应路径，并有望设计出能够提高反应效率的高效催化剂。这样的计算机预测很重要，因为它们大大减少了开发快速有效的化学过程所需的实际实验室时间。

An investigation of the basic mechanisms of a variety of fundamental chemical reactions ranging from pericyclic processes to the reactions of carbenes and singlet oxygen will be conducted. Experimental results will be obtained and compared with frontier molecular orbital and ab initio calculations as appropriate. In the case of pericyclic reactions, attention will be given to the effect of substituents. Experimental isotope effects will be compared to predictions derived from theoretical calculations. Molecular dynamics of forbidden pericyclic reactions will be investigated by variable transition state theory, and ab initio calculations will be performed to generate potential energy surfaces. An investigation of the dynamics of carbene and singlet oxygen reactions will be conducted using statistical mechanics and transition state theory. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Kendall N. Houk at UCLA. The studies will be directed toward providing a better understanding of a number of important chemical reactions. A significant portion of the research project will utilize high speed computers to predict the reaction pathways with the prospect of designing efficient catalysts which are capable of increasing reaction efficiency. Such computer predictions are important since they reduce substantially the actual laboratory time it takes to develop fast and efficient chemical processes.