A. Mañanes

Analysis of the bonding and reactivity of H and the Al13 cluster using density functional concepts

The bonding of hydrogen in the Al13H aggregate is analyzed in the framework of density functional theory using the local density approximation. The interaction between the H-1s orbital and only certain molecular orbitals of Al13 is responsible for the binding. Different measures of the charge transfer give consistent results and predict the stabilization of a sizable amount of electronic charge, about two electrons, around the proton site. The state of the H atom can be described as a negatively charged impurity screened by the surrounding electron gas, similarly to a H impurity embedded in a vacancy in metallic aluminum. Friedel-type oscillations can be appreciated in the screening charge. Local Fukui functions and condensed Fukui indexes associated to the ground state of the cluster Al13 are used as indicators of molecular reactivity. Those indices allow to predict and understand the equilibrium location of H found in the total energy calculations for Al13H.

Ionic vibrational breathing mode of metallic clusters

The energy of the vibrational mode with spherical symmetry, in which the ionic cores oscillate in the radial direction around the equilibrium geometry (ionic breathing mode) is calculated for trivalent (AlN, 2≤N≤50) and monovalent (NaN, 2≤N≤73; CsN, 2≤N≤74) metallic clusters. The ground-state total energy is calculated using density functional theory, with a spherically averaged pseudopotential to describe the ion–electron interaction and optimizing the geometry by the simulated annealing technique. The energy of the ionic mode is calculated by diagonalization of the dynamical matrix including the electronic relaxation in the linear response approximation. The compressibility and bulk modulus of the metallic cluster are obtained from the energies of the monopole oscillations. These energies present a linear behavior on the inverse of the cluster radius, which is analyzed using a semiclassical liquid drop mass formula for the total energy of the clusters and a scaling model. The values of the vibrational frequencies present electronic shell closing effects for the three metals.©1997 John Wiley & Sons, Inc.

Evaporation rates of hot sodium clusters

A scheme based in density functional theory with pseudopotentials is used to obtain the normal modes of vibration of Nan clusters (4 ≤n ≤ 22). The monomer and dimer evaporation rates from thermally excited clusters are obtained in this harmonic approximation. The time evolution of the abundance spectra from an initial uniform mass distribution of hot clusters is studied and its influence in the experimentally observed spectra is discussed.

Atomic and electronic structure of Na10K10Cs n clusters

Density functional theory is used to study the atomic and electronic structures of Na10K10Csn clusters with up to sixty atoms. The simplifying approximation has been made of replacing the external potential of the ionic background by its spherical average about the cluster centre in the iterative process of solving the Kohn-Sham equations for each geometry tested. The search for the equilibrium geometry is performed by employing the technique of simulated annealing. We have always found segregation of Cs atoms to the surface as well as a rather neat separation of different species in different (radial) regions of the cluster. This layering effect appears to be consistent with a tendency to maximize electronegativity differences. When the cluster is big enough, Cs atoms begin to appear also inside the cluster. Those geometrical effects do not perturb the electronic magic numbers well known for pure alkali metal clusters.

Fission barriers for Na N 2+ cluster dissociation

The competition experimentally observed between asymmetric fission and neutral monomer evaporation as dissociation channels of excited doubly charged sodium clusters has been investigated by means of an axially symmetric, fully selfconsistent Kohn-Sham method. Ellipsoidal equilibrium configurations for parent and daughter clusters have been considered using a deformed jellium model.