Slave-boson approach to the size-dependent transition from van der Waals to covalent bonding in Hg_n clusters

We use a microscopic theory to describe the dynamics of the valence electrons in divalent-metal clusters. The theory is based on a many-body model Harniltonian H which takes into account, on the same electronic level, the van der Waals and the covalent bonding. In order to study the ground-state properties of H we have developed an extended slave-boson method. We have studied the bonding character and the degree of electronic delocalization in Hg_n clusters as a function of cluster size. Results show that, for increasing cluster size, an abrupt change occurs in the bond character from van der Waals to covalent bonding at a critical cluster size n_c ~ 10-20. This change also involves a transition from localized to delocalized valence electrons, as a consequence of the competition between both bonding mechanisms.

On the transition from localized to delocalized electronic states in divalent-metal clusters

The transition from van der Waals to covalent bonding, which is expected to occur in divalent-metal clusters with increasing cluster size, is discussed. We propose a model which takes into account, within the same electronic theory, the three main competing contributions, namely the kinetic energy of the electrons, the Coulomb interactions between electrons, and the s \gdw p intraatomic transitions responsible for van der Waals like bonding. The model is solved by taking into account electron correlations using a generalized Gutzwiller approximation (slave boson method). The occurrence of electron localization is studied as a function of the interaction parameters and cluster size.

Theory for the change of bond character in divalent-metal clusters

To determine the size dependence of the bonding in divalent-metal clusters we use a many-electron Hamiltonian describing the interplay between van der Waals (vdW) and covalent interactions. Using a saddle-point slave-boson method and taking into account the size-dependent screening of charge fluctuations, we obtain for Hg_n a sharp transition from vdW to covalent bonding for increasing n. We show also, by solving the model Hamiltonian exactly, that for divalent metals vdW and covalent bonding coexist already in the dimers.