THEORETICAL-STUDIES OF SURFACE-REACTIONS - EMBEDDED-CLUSTER THEORY

A theoretical approach to the description of the electronic structure of molecules adsorbed on solid surfaces and surface reactions is described. The objective is a quantitative, molecular level, understanding of surface processes, including chemisorption energetics, adsorbate structure and reaction mechanisms. The electronic structure problem is formulated as an embedded cluster of atoms in which a localization transformation is used to define the electronic subspace that interacts strongly with the adsorbate and surface region. This permits ab initio SCF and CI calculations of molecular quality to be performed on a portion of the lattice-adsorbate system. Assumptions of the theory are discussed and applications to chemisorption on transition metal substrates are referenced.