Melting and boiling of clusters

Clusters properties depends on their size, the transition from the atom / molecule to the bulk is often smooth and the asymptotic behaviour well understood, but for cluster melting is not the case, where irregular fluctuations are found even for clusters containing more than hundred atoms. A method to measure caloric curves for size selected cluster ions is provided. A plot of the cluster energy as a function of cluster temperature gives the caloric curve and contains all its basic thermodynamic properties. The method consists of two steps: in the first, sodium clusters ions are produced and thermalized. The heat bath was a helium gas of known temperature T, where clusters make so many collisions that they reach thermal equilibrium. Then, the thermalized clusters are extracted, transferred to high vacuum, and mass analysed. In the second step, the internal dominantly vibrational energy E of the cluster is measured by a photofragmentation technique, knowing E and T, the caloric curve E= E(T) can be plotted. As an example the Na 139+ and Na+n study is presented. (nevyjel)