Bimolecular Chemical Reactions in van der Waals Clusters

埃利奥特·伯恩斯坦博士得到了实验物理化学计划的资助，用于研究分离在非常冷的分子团簇中的反应中间产物。这项研究对于评估化学反应中不同溶剂对反应溶质的影响具有重要意义。我们将利用飞行时间质谱学、荧光激发、分散发射和磷光激发技术研究孤立范德华团簇中的双分子化学反应。感兴趣的反应是光诱导的，可分类为：1)溶剂辅助和稳定的电子转移，2)与取代的乙烯加成，以及3)芳环取代。将进行纳秒时间分辨实验，以确定团簇结构和能级，识别潜在的反应体系，并表征产物和过渡态体系。团簇反应动力学将通过皮秒时间相关的单光子计数和各种双色泵浦/探测技术来研究。对这些团簇反应的理论研究将涉及到Bernstein以前应用于双分子团簇反应的RRKM计算的扩展。

Dr. Elliot Bernstein is supported by a grant from The Experimental Physical Chemistry Program to investigate reaction intermediates isolated in very cold molecular clusters. This research is of fundamental importance in assessing the influence which various solvents have on reacting solutes during a chemical reaction. Bimolecular chemical reactions in isolated van der Waals clusters will be studied using time of flight mass spectroscopy, fluorescence excitation, dispersed emission, and phosphorescence excitation techniques. The reactions of interest are photoinduced and can be classified as: 1) solvent assisted and stabilized electron transfer, 2) addition to substituted ethylenes, and 3) aromatic ring substitutions. Nanosecond time resolved experiments will be performed to determine cluster structure and energy levels, to identify the potentially reactive systems, and to characterize the product and transition state systems. Cluster reaction dynamics will be investigated through picosecond time correlated single photon counting and various two color pump/probe techniques. Theoretical studies of these cluster reactions will involve an extension of the RRKM calculations which Bernstein has previously applied to bimolecular cluster reactions.