Studying surface reactivity of transition metals with computational surface science

Computational Surface Science (CSS) techniques, generally based on Density Functional Theory calculations, are increasingly contributing to the understanding of elementary reaction processes on transition metal surfaces, and these techniques are beginning to provide insights that may lead to the design of improved heterogeneous catalysts. CSS thus provides a natural link between the world of fundamental physics and chemistry and the more applied environment of chemical engineering, and it will likely be a useful and powerful tool for practitioners of the latter field for a number of years to come.; In this thesis, the basic principles of the electronic structure calculations that underlie CSS are first introduced. Then, the application of CSS methods to the study and understanding of a number of systems, including methanol synthesis and decomposition on transition metals, subsurface hydrogen formation on nickel crystals, the effect of strain on the formation of subsurface species, and the binding characteristics of diverse adsorbates on rhodium and iridium, is described. Subsequently, the development of a large database of thermochemical and kinetic properties of hydrogen on pure and binary alloy transition metals is discussed, and the implications of this database for improved catalyst design are assessed. Finally, conclusions are drawn about the usefulness of CSS methods for the heterogeneous catalysis community, and suggestions for future work are presented.