Small silver clusters at paramagnetic defects of silica surfaces: A density functional embedded-cluster study

We studied the interaction of small Ag_n clusters (n = 1–4) with paramagnetic defect centers of a dehydroxylated silica surface using an all-electron scalar relativistic density functional method. The surface and adsorption complexes on it were modeled with an accurate quantum mechanics/molecular mechanics (QM/MM) scheme of embedding QM clusters in an elastic polarizable environment, described at the molecular mechanics level (MM). We analyzed two types of frequent point defects as sites for trapping and growing of Ag clusters: a silicon atom with a dangling bond (E′ center), ≡ Si?, and a non-bridging oxygen center (NBO), ≡ Si–O?. The Ag clusters interact with these paramagnetic centers forming strong covalent metal-defect bonds. The high adsorption energy allows one to consider the NBO and E′ sites as traps of single Ag atoms and as centers of cluster growth. We also explored the effect of adsorption on observable electronic properties of the silver clusters and of the defects of the silica surface.