Modelling gold clusters with an empirical many-body potential

Molecular Dynamics Simulated Annealing has been used to probe the structure of small Au clusters consisting of between 2 and 40 atoms. The interatomic interactions within these clusters are described using an empirical Murrell-Mottram many-body potential energy function. Four distinct structural motifs are present in the structures of the predicted global minima, based on octahedra, decahedra, icosahedra and hexagonal prisms. Received 30 September 1999 and Received in final form 23 March 2000     

Computed structures and energetics of ionic neon clusters using DFT correlation corrections

The structural properties of some of the smaller ionic clusters of neon atoms are examined at the post-Hartree-Fock level using a variety of correlation corrections described within a Density Functional treatment. The results of the calculations, and the physical reliability of the method, are discussed in comparison with earlier theoretical results and with the scanty experimental data. The possible presence of a dimeric ion as the core ionic moiety of all the clusters is indicated by the present treatment which also underlines the weaker binding of the outer “shells” of Ne atoms to the central moiety and the rather marked overall charge localization into the central ionic core of the clusters. Received 30 December 1999 and Received in final form 29 February 2000     

Temperature-dependent ionization potential of sodium clusters

The ionization potential of sodium clusters () at a finite temperature is studied using density functional theory and ab initio molecular dynamics. The threshold regions of the photoionization efficiency curves are deduced from the integrated IP distributions, which are obtained from the energy eigenvalues of the highest occupied Kohn-Sham states during molecular dynamics by applying a theoretically well-defined shift. The calculated ionization potentials are directly compared to the experimental values. The energetically best geometry of Na₅₅ is found to be a slightly distorted icosahedron. Received 16 April 1999 and Received in final form 6 July 1999     

Simulation of small positively charged MgO clusters and study of their electronic densities

With the help of ab initio methods the clusters [(MgO)₁₃Mg] ^Q+ are simulated for Q = 0, 1, 2. Then, vacancy clusters [(MgO)₁₂Mg₂] ^Q+ obtained by removing one oxygen atom are computed for Q running from 0 to 4. These clusters exhibit a slight sphericity and generally shorter interatomic distances than in the crystal. The electronic densities variations are studied in function of Q. In particular, it is observed that the electronic density in the oxygen vacancy goes to a maximum when Q = 2. The ionisation potentials vary from approximately 4 to 14 eV when Q varies from 0 to 3, with a more rapid increase from Q = 1 to Q = 2. The stability study of vacancy clusters show that they experience a phase transition when their charge becomes equal to 2, in accordance with the features mentioned above. Received 14 September 1999 and Received in final form 2 December 1999     

The internal energy of small ammonia clusters in a supersonic beam and after scattering off LiF(100)

The photoionization efficiency (PIE) of neutral ammonia clusters is studied as a function of photon energy. From these curves the internal energies of clusters in the incident supersonic beam and of clusters surviving after scattering off a LiF(100) surface are derived. A supersonic expansion of ammonia seeded in He produces small clusters of various size but with uniform kinetic energy of about 285 meV per monomer molecule. The mass distribution of clusters in the jet and of the scattered particles is measured in a reflecting time-of-flight mass spectrometer by single photon photoionization using vacuum ultraviolet (VUV) laser radiation tunable between and . In the incident beam the internal energies of clusters up to n = 15 do not vary significantly and amount to an average of about . After scattering off LiF(100) the internal energy of clusters up to n = 4 increases with fragment size and amounts to about half a monomer binding energy. Received 18 October 1999 and Received in final form 10 December 1999     

Structural characterization of pumice-supported silver-palladium metal clusters by means of XAFS and AWAXS

Silver-palladium bimetallic clusters were synthesized on pumice by the reduction of aqueous solution of metal salts with different Pd:Ag ratios. Used as bimetallic catalysts, in hydrogenation reactions, in situations where molecules can undergo several different reactions, they eliminate undesired reactions and maximize the desired ones. To characterize the structure of these bimetallic catalysts and control if the two metallic elements do mix or not to each other to form an alloy, the structure of the Ag-Pd bimetallic clusters was investigated by means of X-ray-absorption fine-structure spectroscopy (XAFS) and anomalous wide angle X-ray scattering (AWAXS) experiments performed at the European Synchrotron Radiation Facility (ESRF) using the GILDA and the BM16 beamlines. A correlation between Ag and Pd was found but not a clear evidence of alloying. Received: 21 December 1998 / Received in final form: 19 March 1999     

Metal clusters in metal/C thin film nanosystems

Structure of metal clusters and of the C₆₀ matrix in Au/C₆₀ and Cu/C₆₀ nanosystems was investigated by X-ray diffraction. Results support a charge-transfer-type interaction at the metal-C₆₀ interface, which affects the size distribution of metal clusters, favouring interstitial location of metal ions in the fullerite lattice. Received 5 February 1999 and Received in final form 7 July 1999     

Critical size and surface effect of the hydrogen interaction of palladium clusters

Metal hydrides are used for electrochemical or gaseous storage of hydrogen because considerable amounts of hydrogen are reversibly absorbed and desorbed at interstitial sites. Palladium is often used as a model system. Nanophase material is of interest because properties related to the hydrogen absorption are size dependent. In this study, clusters from the size of 55 to 1415 atoms are investigated and compared with bulk Pd. It turns out that not only the amount of hydrogen per palladium that can be intercalated changes but also kinetics and chemical potentials are dependent on the cluster size. The clusters used for this study were chemically synthesised and stabilised by a ligand shell. Received 9 October 1998 and Received in final form 10 May 1999     

Trianionic gold clusters

Using Penning-trap experiments and a shell-correction method incorporating ellipsoidal shape deformations, we investigate the formation and stability patterns of trianionic gold clusters. Theory and experiment are in remarkable agreement concerning appearance sizes and electronic shell effects. In contrast to multiply cationic clusters, decay of the trianionic gold clusters occurs primarily via electron autodetachment and tunneling through a Coulomb barrier, rather than via fission. Received 9 January 2001     

Can we rationalize the structure of small silicon-carbon clusters?

A theoretical study of clusters with using density functional theory is presented. Tests of various functionals demonstrate that local spin density approximation (LSDA) is the most adequate functional for the study of these systems. Structures, vibrational frequencies, and IR intensities of the lowest energy isomer of the studied clusters obtained using LSDA are described, and the unusual properties of the Si-C clusters are discussed. A quantitative analysis of the obtained structures was carried out, and relations between the coordinations, interatomic distances, and angles observed in the Si-C clusters were obtained through introduction of the notion of coordination. This analysis also shows that the carbon atoms mainly exhibit sp and sp² hybridizations, and that a majority of silicon atoms do not hybridize. This study is the fi rst step of the implementation of a semi-empirical potential, which would describe the moderately small Si-C clusters. Received: 20 October 1997 / Received in final form: 16 December 1997 / Accepted: 17 December 1997     

Influence of covalence and anion symmetry on the structure of small metal hydroxide clusters: Sodium versus silver hydroxide

An ab initio study of the Na_n(OH)_n, Na_n(OH)_n-1 ⁺, Ag_n(OH)_n, and Ag_n(OH)_n-1 ⁺ clusters with n up to four is presented. The results of this study show that, in accordance with experimental observations, the sodium hydroxide clusters are almost purely ionic, while the Ag-O bond exhibits a significant covalent character. The perturbation caused by the non-spherical OH^- group relatively to an atomic anion, as well as the influence on structures and energies of the covalent character of the metal-oxygen bond are determined. The appearance of metal-metal bonds in the silver hydroxide clusters is also discussed. Finally, the theoretical results obtained on the Na-OH clusters are compared to experimental results available on the dissociation of the Na_n(OH)_n-1 ⁺ clusters. Received 9 August 1999 and Received in final form 1st December 1999     

Effects of solvation on dissociative electron attachment to methyl iodide clusters

Using laser photoelectron attachment to methyl iodide clusters in a differentially-pumped seeded supersonic helium beam and mass spectrometric ion detection, we have measured the rate coefficients for formation of (q = 0-2) ions over the electron energy range 0-100 meV with an effective energy width of about 2.5 meV. Whereas a prominent vibrational Feshbach resonance just below the onset for the C-I stretch vibration ( ) is observed for dissociative attachment to monomers (yielding I^- ions), only weak and broad structure, shifted to lower energies, is detected for formation of ions and essentially no structure is left in the attachment spectrum for . These observations are interpreted by model R-matrix calculations which successfully describe the DA cross-section for the monomer and qualitatively recover the trend observed for cluster ion formation. For the clusters, the effects of increased electron-target long-range interaction and of solvation as well as coupling to soft vibrational modes lead to strong broadening and shifting of the vibrational Feshbach resonance and, ultimately, to its disappearance. Received 29 November 1999 and Received in final form 14 January 2000     

Critical dynamics in clusters of noble gas atoms

The multi-fragmentation dynamics of noble gas atomic clusters is considered for different statistically distributed deposited energies. The conditions giving rise to the development of criticality in the cluster evolution are revealed from an analysis of the signals in the fragment mass distribution. The time dependence of the observables related to critical exponents is studied. It is demonstrated that in a certain regime the cluster exhibits a behavior which can be identified as the precursor of a second-order liquid-gas phase transition. Received 1st September 1998 and Received in final form 14 January 1999     

Percolation with constraints in the highly polarizable oxide KTaO<Subscript>3</Subscript>:Li

Experimental data on the temperature and electric field dependence of the Second Harmonic Generation Intensity in the solid solution KTaO₃:Li is analyzed in the framework of a new percolation-type approach which considers the history of cluster formation averaged over a large number of samples. In order to take into account that two cluster dipole moments turn when joining clusters together, a constraint is imposed on the cluster growth. This constraint leads to cluster-size saturation just after the percolation threshold. Owing to this circumstance, the connected cluster coexists with free clusters in some range of the impurity concentration and temperature. There is qualitative agreement between the computational results and experiments on Second Harmonic Generation intensities. The algorithm was written in C++ which allowed realistic computations to be performed on a standard PC. Received 26 August 1999 and Received in final form 27 December 1999     

Static electric dipole polarizabilities of Na clusters

The static electric dipole polarizability of Na _N clusters with even N has been calculated in a collective, axially averaged and a three-dimensional, finite-field approach for , including the ionic structure of the clusters. The validity of a collective model for the static response of small systems is demonstrated. Our density functional calculations verify the trends and fine structure seen in a recent experiment. A pseudopotential that reproduces the experimental bulk bond length and atomic energy levels leads to a substantial increase in the calculated polarizabilities, in better agreement with experiment. We relate remaining differences in the magnitude of the theoretical and experimental polarizabilities to the finite temperature present in the experiments. Received 8 November 1999     

Simulating the thermal stability and phase changes of small carbon clusters and fullerenes

The thermal stability, phases and phase changes of small carbon clusters and fullerenes are investigated by constant energy Molecular Dynamics simulations performed over a wide range of temperatures, i.e., from to above the melting point of graphitic carbon. The covalent bonds between the carbon atoms in the clusters are represented by the many-body Tersoff potential. The zero temperature structural characteristics of the clusters, i.e., the minimum energy structures as well as the isomer hierarchy can be rationalized in terms of the interplay between the strain energy (due to the surface curvature) and the number of dangling bonds in the cluster. Minimization of the strain energy opposes the formation of cage structures whereas minimization of the number of dangling bonds favors it. To obtain a reliable picture of the processes experienced by carbon clusters as a function of temperature, both thermal and dynamical characteristics of the clusters are carefully analyzed. We find that higher excitation temperatures are required for producing structural transformations in the minimum energy structures than in higher lying isomers. We have also been able to unambiguously identify some structural changes of the clusters occurring at temperatures well below the melting-like transition. On the other hand, the melting-like transition is interrupted before completion, i.e., the thermal decomposition of the clusters (evaporation or ejection of or units) occurs, from highly excited configurations, before the clusters have fully developed a liquid-like phase. Comparison with experiments on the thermal decomposition of and a discussion of the possible implications of our results on the growth mechanisms leading to the formation of different carbon structures are included. Received: 25 March 1998 / Received in final form: 30 October 1998     

A computer simulation study of the ground-state configurations of Fe and Fe-Al clusters

Using the noncentral embedded atom model potential recently proposed by Besson and Morillo for bulk alloys (), we performed computer simulations to predict the ground-state configurations of and clusters (). The computed structures of clusters are in general agreement with such theoretical results as have been obtained by density functional calculations (i.e. for ). The results for Fe-rich clusters show surface segregation of Al, which is in keeping with the findings of a previous study of clusters. Received 29 April 1999     

Assembling of hydrogenated aluminum clusters

The electronic and atomic structure of Al₁₃H has been studied using Density Functional Theory. Al₁₃H has closed electronic shells. This makes the cluster very stable and suggests that it could be a candidate to form cluster assembled solids. The interaction between two Al₁₃H clusters was analyzed and we found that the two units preserve their identities in the dimer. A cubic-like solid phase assembled from Al₁₃H units was then modeled. In that solid the clusters retain much of their identity. Molecular dynamics runs show that the structure of the assembled solid is stable at least up to 150 K. A favorable relative orientation of the clusters with respect to their neighbors is critical for the stability of that solid. Received 21 November 2000     

Ground-state geometries and stability of NaMg clusters using ab initio molecular dynamics method

The ground-state geometries, energetics and the stability of ( n =1-12) clusters are studied using ab initio molecular dynamics method. Our results indicate that the ground-state geometries of large clusters () are different from those of clusters where a trivalent impurity Al is added to the same monovalent host Na. Other features observed are an early appearance of 3-dimensional structure and a pentagonal growth path from n =6 up to n =11. As expected, the ground-state geometry of is not an icosahedron but can be viewed as a distorted form of one of the low lying geometries of cluster. In the energetically favored structures impurity atom Mg is never located at the center of the cluster. The stability analysis based on the energetics shows (8 valence electrons) to be the most stable. In addition there is a remarkable even-odd pattern observed in the dissociation energy and the second difference in energy which is absent in earlier studies of and clusters. Received: 16 September 1998 / Received in final form: 15 February 1999     

Optical properties of gold metal clusters: A time-dependent local-density-approximation investigation

The optical response of free and matrix-embedded gold metal clusters Au_N is investigated in the framework of the time-dependent local-density-approximation (TDLDA). The characteristics of the surface plasmon resonance are carefully analyzed as a function of the model parameters and the particle radius. The strong influence of the frequency-dependence of the 5d core-electron dielectric function in the vicinity of the interband threshold is emphasized. The size evolution of the Mie-frequency in free gold clusters exhibits a noticeable blue-shift trend as the particle size decreases, much stronger than in silver clusters. The width and shape of the resonance, essentially ruled by the decay via the interband transitions, are found closely correlated to the imaginary component of the core-electron dielectric function. In presence of a surrounding matrix the blue-shift trend is largely rubbed out. Agreement with recent experimental results on size-selected gold clusters embedded in an alumina matrix may be achieved by taking into account the porosity effects at the metal/matrix interface. The comparison with the predictions of classical models is also provided. Received: 9 March 1998 / Revised: 5 June 1998 / Accepted: 3 July 1998