Mechanistic and Exploratory Organic Photochemistry

在化学系有机动力学项目的资助下，威斯康星大学麦迪逊分校的霍华德·E·齐默尔曼教授将通过计算方法理解超表面和无辐射过程，以及通过计算支持的系统方法来研究有机光化学的力学基础。该项目包括研究预测替代过渡结构适应反应物晶格的能力的方法(即确定哪些产物在固态光反应中是可行的)，研究激发超表面上的势垒或无辐射衰变过程是否在某些特定情况下控制光产物的形成，以及研究聚合物基质作为分子光化学的约束。进行化学反应的阶段--晶体、无定形固体、液体或气体--可以决定反应的结果。晶体约束通常非常大，但通常不容易预测。这项工作将开发一种使用计算技术预测晶体中光诱导反应的有利反应路径的方法。其他计算技术将允许理解约束较少的环境中的反应细节

With funding from the Organic Dynamics Program of the Chemistry Division, Professor Howard E. Zimmerman of the University of Wisconsin - Madison will study mechanistic fundamentals of organic photochemistry, via computational approaches to understanding of hypersurfaces and radiationless processes, and computationally supported systematic approaches to solid state photochemistry. The project includes examination of ways to predict the ability of alternative transition structures to fit in reactant crystal lattices (i.e. ways to determine what products are viable in solid state photoreactions), studies of whether barriers on excited hypersurfaces or radiationless decay processes control photoproduct formation in certain specific instances, and a study of polymer matrices as constraints on molecular photochemistry. The phase in which a chemical reaction is conducted - crystal, amorphous solid, liquid, or gas - can determine the outcome of the reaction. Crystal constraints are frequently very great but are not usually readily predictable. This work will develop a way of prediction of favored reaction pathways for light-induced reactions in crystals using computational techniques. Other computational techniques will allow understanding of details of reactions in less constrained environments