The liquid state of large clusters with pairwise atomic interactions

Formation of the liquid state for clusters with a pair interaction between atoms is examined within the framework of the void model, in which configurational excitation of atoms results from formation of voids. Void parameters are found from computer simulation by molecular dynamics methods for Lennard-Jones clusters and from real thermodynamic parameters of the liquid states of condensed inert gases. Phase transitions are analyzed in terms of two aggregate states. This information allows us to divide the entropy jump during the solid-liquid phase transitions in two parts. so that one corresponds to configuration excitation at zero temperature, and the other is a contribution from thermal vibrations of atoms. The latter part contributes from approximately 40% for Lennard-Jones clusters consisting of 13 and 55 atoms up to 56% for bulk inert gases. These magnitudes explain the validity of melting criteria based on thermal motion of atoms, even though this phase transition results from configurational excitation of ensembles of bound atoms. It is shown that the void concept allows us to analyze various aspects of the liquid state of clusters including the existence of the freezing temperature below which no metastable liquid state exists, and the properties of glassy states which may exist below the freezing point. (c) 2005 Elsevier B.V. All rights reserved.