M. P. Iñiguez

Electronic and atomic structure of Na, Mg, Al and Pb clusters

Density functional theory is used to study the electronic and atomic structure of small clusters of Na, Mg, Al and Pb. We study the quantityEN−1–EN, which has relevance to the processes of cluster growth and evaporation (EN is the total energy of the cluster withN atoms). By comparing the results of the jellium model with those of a more realistic model (although still simple) we are able to appreciate “structural” effects beyond the “electronic-shell effects” which form the essence of the predictions of the jellium model. The calculations predict formation of atomic shells and appreciable reconstruction as the cluster grows.

Molecular dynamics study of cluster impact on the (001) and (110) surfaces of fcc metals

Molecular dynamics simulations of the impact deposition of metal clusters on fcc metal surfaces are presented. Two-dimensional elongated islands are formed when the incident cluster travels parallel to the surface. For perpendicular incidence the results of the impact event are very sensitive to the relative cohesive properties of the cluster and substrate atoms.

Immersion of hydrogen atoms in aluminium clusters: a density functional pseudopotential study

The immersion of a H atom at the centre of AlN clusters with 8≦N≦21 has been studied using the density functional formalism and a pseudopotential averaged about the cluster centre. The immersion energy is negative forN≦12, due to the fact that the corresponding pure Al clusters contain a central vacancy, which shows a strong affinity for the H atom. For larger sizes the immersion energy is positive (with a few exceptions), since the H atom must displace a central Al atom to the cluster surface, and it shows non negligible size oscillations.

Distribution of interatomic distances in large metallic clusters

Spherically averaged pseudopotential (SAPS) calculations have been done for Mgn clusters, withn up to 250 within the framework of density functional theory. The electronic structure is computed resorting to the Thomas-Fermi-Dirac-Weizsäcker (TFDW) approximation for the kinetic energy. The equilibrium geometries have been obtained by minimizing the total cluster energy with respect to the atomic positions using the steepest-descent method. The ground state geometries obtained in this way are formed by spherical atomic shells, the number of them increasing with cluster size, up to a number of four for the biggest sizes considered here. An analysis of the distribution of the interatomic distances shows that the more internal is the shell, the more contracted are the interatomic distances. This effect diminishes progressively with increasing cluster size. For the purpose of comparison, similar calculations have been done with Csn clusters in the same size range, allowing us to reproduce previous results obtained using a more elaborated density functional technique (Kohn-Sham method). The inhomogeneous contraction of interatomic distances then appears as a general fact for simple metallic clusters and not only for alkaline ones.

Coulomb explosion of charged jellium clusters

The Density Functional Formalism is used to calculate the minimum number of atoms (Nc) a multiply charged jellium-like spherical cluster must contain to be stable against coulomb explosion into two smaller fragments. In the case of alkaline clusters, which are systems for which the jellium model can be applied, we findNc equal to 31 and 23 for the explosion of NaN2+ and CsN2+ respectively, in good agreement with the experimental value ofNc = 18 for CsN2+. Calculated critical numbers for triply and tetracharged Cs clusters are 108 and 323 respectively. In addition the model predicts that the most favourable fragmentation channel is the ejection of a singly charged monomer.

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.

Stability of isomeric Na n clusters

A method which combines density functional theory and the use of pseudopotentials is applied to obtain ground state and low-lying metastable geometries of Nan clusters (7≤n≤40). The large variation in the magnitude of energy gaps between isomers suggests that the melting temperature is not a simple monotonous function of size. A detailed study of the differences between electronically stabilized (n=8, 20, 40) and structurally stabilized (n=13) clusters suggests some clues to understand the intriguing behaviour of Na13.

Electron density and atomic relaxation around a vacancy in a small metal particle

The electron density in an ideal vacancy placed at the center of a small Aluminium microparticle has been studied as a function of the number of atoms in the microparticle. In these circumstances one can conclude that the perturbation of the density is localized in the close neighborhood of the vacancy and is nearly independent of the particle size. Then relaxation of the nearest neighbours of the vacancy was allowed. This relaxation was found to be small, but its sign depends on particle size. For particles larger than ∼100 atoms the relaxation is towards the vacancy, as for a vacancy in bulk Aluminium. But for smaller particles, the relaxation is away from the vacancy. This relaxation suggests a nontrivial size dependence of the energy of vacancy formation.

Molecular dynamics study of A18B lennard-jones clusters

Low temperature structures, melting and evaporation temperatures of A18B clusters with Lennard-Jones interactions have been studied using Molecular Dynamics simulations for different values of the parameters representing (a) the size ratio between A and B atoms, and (b) the ratio between the strengths of the A - B and A - A interactions.