Theory of chemisorption and reactions on metal surfaces

A review of theoretical methods used to describe chemisorption and adsorbate reactions on metal surfaces is contained in this report. A comprehensive perspective on state-of-the-art electronic structure methods suitable for these problems and a review of applications that illustrate current capabilities of theory are presented. First-principles ab initio and density functional methods and semiempirical approaches that permit the calculation of adsorbate energetics, structure and spectra are emphasized. In addition to the chemisorption of molecules and molecular fragments, applications include gas-surface reactions, dissociative processes and surface reactions involving coadsorbed species. Many of the applications are relevant to transition metal heterogeneous catalysis. Both slab and atomic cluster methods are described. Methods are critiqued, with reference to published applications, to illustrate capabilities and limitations of different approaches. An extensive compendium of applications is included.