The free energy of a 600-atom Lennard-Jones cluster is calculated as a function of surface and bulk crystallinity in order to study the structural transformations that occur in the core of medium sized clusters. Within the order parameter range studied, we find the existence of two free energy minima at temperatures near freezing. One minimum, at low values of both bulk and surface order, belongs to the liquid phase. The second minimum exhibits a highly ordered core with a disordered surface and is related to structures containing a single fcc-tetrahedral subunit, with an edge length of seven atoms (l=7), located in the particle core. At lower temperatures, a third minimum appears at intermediate values of the bulk order parameter which is shown to be related to the formation of multiple l=6 tetrahedra in the core of the cluster. We also use molecular dynamics simulations to follow a series of nucleation events and find that the clusters freeze to structures containing l=5, 6, 7, and 8 sized tetrahedra as well as those containing no tetrahedral units. The structural correlations between bulk and surface order with the size of the tetrahedral units in the cluster core are examined. Finally, the relationships between the formation of fcc tetrahedral subunits in the core, the phase behavior of medium sized clusters and the nucleation of noncrystalline global structures such as icosahedra and decahedra are discussed.

A diverse range of linear polysiloxane-based ionic polymers that are hydrophobic and highly flexible can be obtained by substituting the polymers with varying amounts of ionic centers. The materials can be highly crystalline solids, amorphous soft solids, poly(ionic) liquids or viscous polymer liquids. A key to understanding how structural variations can lead to these different materials is the establishment of correlations between the physical (dynamic and static) properties and the structures of the polymers at different distance scales. This short review provides such correlations by examining the influence of structural properties (such as molecular weights, ion pair contents, and ion types) on key bulk properties of the materials.