Adsorption at Nanostructured Surfaces from First Principles

Nanostructured surfaces often exhibit adsorption properties that are distinctly different from those of flat surfaces. This is the reason for the current interest in the adsorption at nanostructured surfaces, both from the fundamental as well as the applied point of view. In this review, the theoretical modeling and the computational treatment of the interaction of molecules with nanostructured surfaces will be discussed. Since the adsorption of molecules at surfaces involves bond-making and bond-breaking processes, a quantum mechanical description is required which is associated with a relatively large computational effort. Still, because of the progress in the computer power and the development of efficient electronic structure algorithms rather complex molecule-surface systems can be treated from first principles, i.e., without invoking any empirical parameters. The systems addressed in this review include stepped surfaces, supported clusters, surface alloys, nanostructures formed by adsorbate layers, and the dynamics of adsorption on at such a layer. Special emphasis will be put on establishing a microscopic understanding of the specific properties of nanostructured surfaces