Surface melting of clusters and implications for bulk matter

Abstract

Surface melting on clusters is investigated by a combination of analytic modeling and computer simulation. Homogeneous argonlike clusters bound by Lennard-Jones forces and Cu-like clusters bound by ‘‘embedded-atom’’ potentials are the systems considered. Molecular-dynamics calculations have been carried out for clusters with 40–147 atoms. Well below the bulk melting temperature, the surfaces become very soft, exhibiting well-defined diffusion constants even while the cores remain nearly rigid and solidlike. The simulations, particularly animations, of atomic motion reveal that the surface melting is associated not with amorphous, random surface structures in constant, irregular motion, but rather with large-amplitude, organized, collective motion of most of the surface atoms accompanied by a few detached atoms (‘‘floaters’’) and holes. At any time, a few of the surface atoms are out of the surface layer, leaving vacancies; these promoted particles wander diffusively, the holes also but less so; the floaters occasionally exchange with atoms in the surface layer. This result is the basis for an analytic, statistical model. The caloric curves, particularly the latent heats, together with the results from an analytical model, show that surface melting of clusters is a ‘‘phase change’’ different from the homogeneous melting of clusters.