Size-dependent properties of transition metal clusters: from molecules to crystals and surfaces – computational studies with the program ParaGauss

Abstract

In the so-called scalable regime the size-dependent behavior of the physical and chemical properties of transition metal clusters is described by scaling relationships. For most quantities this scalable regime is reached for cluster sizes between a few tens and a few hundreds of atoms, hence for systems for which an accurate treatment by density functional theory is still feasible. Thus, by invoking scaling relations one is able to obtain properties of very large nanoparticles and even the bulk limit from the results of a series of smaller cluster models. In this invited review we illustrate this strategy by exploiting results from computational studies that mostly were carried out with the density functional theory software ParaGauss. We address mainly the size-dependent behavior of the properties of transition metal clusters. To this end, we first present benchmark studies probing various approximations that are used in such density functional calculations. Subsequently we show how physical insight may be gained by exploring less understood types of systems. These applications range from bare clusters to nanoislands and nanoalloys to adsorption complexes.