Analogies among chemical properties of metal surfaces, organometallic molecules, and enzymes

Abstract The theorist who plans to study the chemical properties of surfaces from a fundamental electronic point of view is presented with a number of difficult problems. For example, if one focuses on heterogeneous catalysis by metal particles dispersed on a support,1 should the electronic structure of the particles be viewed in terms of the band-structure theory of solid state physics or in terms of the chemical-bond concept of inorganic chemistry? What are the most significant configurations of adsorbates which are precursors to heterogeneous reactivity? Does the supporting material affect chemisorption and catalytic activity? The theorist who calculates electronic structure is accustomed to having the positions and configurations of atoms in a molecule or solid as input to the calculation. Unfortunately, detailed structural information for heterogeneous catalysts is frequently unavailable and is just beginning to be a subject of experimental investigation. In contrast, the molecular structures of transitionmetal coordination complexes involved in ho mogeneous catalysis2 and enzymes involved in biocatalysis are often known to reasonable accuracy.