Nanosolids, slushes, and nanoliquids: Characterization of nanophases in metal clusters and nanoparticles

One of the keys to understanding the emergent behavior of complex materials and nanoparticles is understanding their phases. Understanding the phases of nanomaterials involves new concepts not present in bulk materials; for example, the phases of nanoparticles are quantum mechanical even when no hydrogen or helium is present. To understand these phases better, molecular dynamics (MD) simulations on size-selected particles employing a realistic analytic many-body potential based on quantum mechanical nanoparticle calculations have been performed to study the temperature-dependent properties and melting transitions of free Al_n clusters and nanoparticles with n = 10-300 from 200 to 1700 K. By analyzing properties of the particles such as specific heat capacity (c), radius of gyration, volume, coefficient of thermal expansion (β), and isothermal compressibility (κ), we developed operational definitions of the solid, slush, and liquid states of metal clusters and nanoparticles. Applying the definitions, which are based on the temperature dependences of c, β, and In κ, we determined the temperature domains of the solid, slush, and liquid states of the Al_n particles. The results show that Al_n clusters (n ≤ 18, diameter of less than 1 nm) are more like molecules, and it is more appropriate to say that they have no melting transition, but Al_n nanoparticles (n ≥ 19, diameter of more than 1 nm) do have a melting transition and are in the liquid state above 900-1000 K. However, all aluminum nanoparticles have a wide temperature interval corresponding to the slush state in which the solid and liquid states coexist in equilibrium, unlike a bulk material where coexistence occurs only at a single temperature (for a given pressure). The commonly accepted operational marker of the melting temperature, namely, the peak position of c, is not unambiguous and not appropriate for characterizing the melting transition for aluminum particles with the exception of a few particle sizes that have a single sharp peak (as a function of temperature) in each of the three properties, c, β, and In κ.