Intrinsic Barriers as a Guide to Rates and Mechanisms of Reactions on Solid Surfaces

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ABSTRACT CTS 9610115 Richard I. Masel Professor Richard I. Masel, of the University of Illinois, Urbana-Champaign, is being funded by the Chemical Reactions Processes-Kinetics and Catalysis program to continue his studies of adsorption of small organic molecules on model transition metal surfaces. He will continue to develop a theoretical approach to predicting surface chemical mechanisms. The basic hypothesis of the theoretical model is that intrinsic barriers calculated for decomposition reactions in the gas phase are equal to the intrinsic barriers for those decompositions on surfaces. Experimentally, the model is tested with EELS and TPD spectroscopies. In this work, Masel proposes to do more detailed characterization of the intrinsic barriers for C-C, C-O, C-H and O-H bond scissions, in terms of parameters such as substituent groups in the organic molecules or presence of coadsorbates, and nature of the chemisorbing surface. It is focused on the measurement of heats of reaction, bond energies, and intrinsic activation barriers for specific test reactions, for which model predictions will be made with the aid of computational quantum chemistry. The role of net charges in the intrinsic barrier model will also be assessed. This research is of major significance for the theory and practice of catalysis and surface chemistry.