Intramolecular Dynamics of Organic Reactions

在有机化学和高分子化学项目的支持下，康奈尔大学化学和化学生物学系的巴里·K·卡彭特教授正在研究有机反应的分子内动力学。通过从头算电子结构理论、分子动力学模拟和实验有机化学的结合，卡彭特教授解决了什么因素控制在热和光化学反应中产生的活性中间体的行为的问题，包括自由基离子、卡宾和双自由基。正在研究的具体问题包括：是什么控制了在反应路径上遇到分叉点的分子的行为；是什么控制了中间体发现自己的势能井深度，反应动力学如何取决于井深；可以开发什么理论方法来允许非专家探索有机反应机理的动力学问题；什么类型的实验证据提供了传统过渡态理论(TST)行为和非TST动力学行为之间最明显的区别。要想详细、基本地理解有机反应是如何发生的，需要将实验和理论/计算方法相结合，理论提出了合成和研究的重要分子，而对各种有机反应的研究反过来又提出了理解它们所需的理论方法和/或进展。康奈尔大学化学和化学生物学系的巴里·K·卡彭特教授进行了合成和理论研究，旨在解决在化学反应过程中产生的高活性中间体的反应性，这些中间体只存在很短的时间。通过这些研究，卡彭特教授为我们对分子如何反应的基本理解做出了贡献，并提供了其他人适用的计算工具，以继续发展关于有机化学反应的知识。

With the support of the Organic and Macromolecular Chemistry Program, Professor Barry K. Carpenter, of the Department of Chemistry and Chemical Biology at Cornell University, is studying the intramolecular dynamics of organic reactions. Through a combination of ab initio electronic structure theory, molecular dynamics simulations, and experimental organic chemistry, Professor Carpenter addresses the question of what factors control the behavior of reactive intermediates, including radical ions, carbenes, and biradicals, generated in thermal and photochemical reactions. Specific questions under investigation include what controls the behavior of molecules that encounter bifurcation points on their reaction paths; what controls the potential energy well depth in which an intermediate finds itself, and how does the reaction dynamics depend on the well depth; what theoretical methods can be developed to allow nonexperts to explore the dynamic issues of an organic reaction mechanism; and what kinds of experimental evidence provide the clearest distinction between traditional transition state theory (TST) behavior and behavior governed by non-TST dynamics.Development of a detailed, fundamental understanding of how organic reactions occur requires a combination of experimental and theoretical/calculational approaches, with theory suggesting important molecules for synthesis and study and with the study of various organic reactions in turn suggesting theoretical approaches and/or advances necessary to understand them. Professor Barry K. Carpenter, of the Deparment of Chemistry and Chemical Biology at Cornell University, carries out both synthetic and theoretical studies designed to address the reactivity of highly reactive intermediates, of only fleeting existence, generated in the course of chemical reactions. Through these studies, Professor Carpenter contributes to our fundamental understanding of how molecules react and provides calculational tools applicable by others in the continuing advancement of knowledge about organic chemical reactions.