Mathematical Sciences: Probing Transition States on Surfaces

9401276 Gellman这个研究项目，在分析和表面化学计划的支持下，应用物理有机化学的概念来研究表面反应动力学。 几个表面反应的过渡态的电子结构将通过氟取代来探测。 取代基对氢化物消除，去质子化，和铜表面上的烷基偶联等反应的影响将使用电子光谱和动力学探针进行探索。 量子化学计算将进行比较的动力学和热力学测量的结果，形成大部分的拟议工作。 该方法可广泛应用于催化和电化学反应化学的研究。 理解表面化学反应中过渡态的能量学将有助于设计有效的催化体系。 这个研究项目，在分析和表面化学计划的支持下，解决了这个问题的实验和理论。 通过使用物理有机化学的成熟方法，取代基效应将被用来探测一些重要的表面化学反应的过渡态。 ***

9401276 Gellman This research project, supported in the Analytical and Surface Chemistry Program, applies the concepts of physical organic chemistry to the study of surface reaction kinetics. The electronic structure of the transition state of several surface reactions will be probed by fluorine substitution. The substituent effect on such reactions as hydride elimination, deprotonation, and alkyl coupling on copper surfaces will be explored using electron spectroscopic and kinetic probes. Quantum chemical calculations will be carried out to compare with the results of the kinetic and thermodynamic measurements which form the bulk of the proposed work. This approach may be widely applicable to the study of catalytic and electrochemical reaction chemistry. %%% An understanding of the energetics of the transition state in surface chemical reactions would help to design efficient catalytic systems. This research project, supported in the Analytical and Suface Chemistry Program, addresses this question experimentally and theoretically. By using proven methods of physical organic chemistry, the substituent effect will be exploited to probe the transition state in a number of important surface chemical reactions. ***