Optical spectroscopy on size selected gold clusters deposited in rare gas matrices

We report on the successful “soft-landing” of size selected Au trimers in solid Krypton matrices. The Au cations are produced by sputtering, mass-selected in a quadrupole mass spectrometer, co-deposited with Krypton on a cooled CaF₂ substrate, and neutralized by low energy electrons. The deposition of low kinetic energy cations (10 eV) gives rise to strong excitation bands, detected by the emitted fluorescence light, which are unambiguously attributed to Au trimers. The deposition and fragmentation process is qualitatively discussed.     

Magic numbers of large rare gas clusters

The superior stability of closed-shell icosahedral structures is evident from size distributions of argon, krypton and xenon cluster ions in the size range 100?n?1000.     

Density functional theory of the collective electronic excitations in NanKn clusters

The collective electronic response of Na_nK_n clusters has been studied for some model structures. In their low-temperature lowest-energy structure, those clusters have all the K atoms on the surface. The collective oscillation frequencies for clusters with the K atoms segregated to the surface are red-shifted with respect to the corresponding frequencies for isomers with a very similar underlying skeleton but with the Na atoms segregated to the surface. The collective frequency varies smoothly with respect to the degree of relative segregation. These results may be useful in the analysis of the collective response of large alloy clusters and microcrystals. © 1995 John Wiley & Sons, Inc.     

Magnetic properties of rare earth clusters

We report results of Stern-Gerlach deflection experiments on terbium clusters, which resemble earlier results for gadolinium clusters. As in gadolinium, we observe two distinct behaviors: clusters that are superparamagnetic and clusters that are described by a locked-moment model. The magnetic behavior is highly size dependent. Certain clusters make a transition from locked-moment to superparamagnetic behavior with increasing temperature and, in this process, exhibit an intermediate behavior. Both superparamagnetic and locked-moment clusters have magnetic moments per atom well below the bulk value. We show that oxygen atoms attached to the clusters have little effect on the clusters' magnetic properties and are not responsible for the two distinct behaviors observed in rare earth clusters. We also present preliminary results from studies on dysprosium clusters.     

Thermal electronic properties of alkali clusters

We apply the finite-temperature Kohn-Sham method to alkali metal clusters, using the spherical jellium model and treating the valence electrons as a canonical system in the heat bath of the ions. We study the shell effects in the total free energyF(N) and the entropyS(N) for neutral clusters containingN atoms. Their strongest temperature dependence is due to the finite ground-state valueS ₀>0 of the electronic entropy for non-magic clusters. It leads to a decreasing amplitude and an increasing smear-out of the saw-tooth structure in the first difference Δ₁ F(N)=F(N?1)?F(N) with increasing temperatureT and cluster sizeN.     

Structural and electronic properties of compound metal clusters

The equilibrium geometries, relative stabilities, and vertical ionization potentials of compound clusters involving Li _n , Na, Mg, and Al atoms have been calculated using ab initio self-consistent field linear combination of atomic orbitals — molecular orbital (SCF-LCAO-MO) method. The exchange energies are calculated exactly using the unrestricted Hartree-Fock (UHF) method whereas the correlation correction is included within the framework of configuration interaction involving pair excitations of valence electrons. While the later correction has no significant effect on the equilibrium geometries of clusters, it is essential for the understanding of relative stabilities. Clusters with even numbers of electrons are found to be more stable than those with odd numbers of electrons regardless of their charge state and atomic composition. The equilibrium geometries of homo-nuclear clusters can be significantly altered by replacing one of its constituent atoms with a hetero-nuclear atom. The role of electronic structure on the geometries and stabilities of compound clusters is discussed.     

Fragmentation of large ionized clusters of rare gas atoms

Molecular dynamics is used to examine the fragmentation of clusters of rare gas atoms after ionization. The cohesive energy is given by a quantum mechanical model with a delocalized hole. Very small clusters dissociate entirely into single atoms and a positively charged dimer. Larger clusters (e.g. Ne₁₃, Xe₁₃ and Ne₅₅) first eject rapid atoms, then thermalize and evaporate further atoms, which strongly decreases their size. Very large clusters (e.g. Xe₅₅) are only heated up after ionization and do not loose atoms. Thus the peaks in mass spectra do not show the atomic shell structure of neutral clusters up to rather large cluster sizes. Instead the stability of ionized clusters is reflected.     

Fluorescence of rare gas clusters excited with synchrotron radiation

A cluster beam experiment for fluorescence measurements on rare gas clusters has been built up. First results on the evolution of energy levels of neutral krypton clusters with a cluster size between 200–8500 atoms/cluster are reported. The well known bulk excitons of solid krypton do not merge into the first atomic lines and appear only in clusters larger than 300 atoms/cluster. Smaller clusters absorb only at energies which fit well with surface excitons of the solid.     

Structural and electronic properties of hydrated MgO nanotube clusters

Hydrated MgO nanotube clusters are constructed and studied by the density functional theory at the B3LYP/6-31G(d) level. A strong exothermicity chemisorption reactivity of MgO nanotube clusters with water, which releases 137.5–171.8 kJ/mol. The averaged charge of Mg ions is steady, and presents a stronger ionic bonding. Mg ions are more sensitive to the coordination number. For the reaction of water onto clusters, electronic properties of hydrated clusters have remarkable change compared with anhydrous clusters.     

Theory for excess electrons in clusters of rare gas atoms

An exact theory for excess electrons in clusters of rare gas atoms is limited to small sizes,n < 20, because of many body polarization interactions which make it necessary to solve a large system of linear equations. We present a simple dielectric screening approximation, which avoids this difficulty and which is in very good agreement with the exact calculation. This approximation can be used to examine the excitation energies of excess electrons and exciton energies in large clusters. A new atomic structure is proposed for a cluster of 12 Xe atoms, resulting in an increased binding energy for the excess electron, which is larger than the electron affinity of a cluster of 13 atoms. This might explain the relatively large abundance of Xe ₁₂ ^? observed in the experiment.     

General properties of the electronic structure of alkali metal clusters and Ia-IIa mixed clusters

The results of the systematic ab-initio CI investigation of neutral and charged Li _n , Na _n , BeLi _k and MgNa _k clusters are summarized and analyzed. The general characteristic features of the electronic structure are pointed out:a) The participation of the atomic orbitals, which are empty in Ia and IIa metal atoms, allows for a higher valency of these atoms in clusters.b) Jahn-Teller and pseudo-Jahn-Teller effects strongly influence the electronic and geometric structure of clusters.c) Deformations of cluster geometry can lead to biradicaloid structures with higher spin multiplicity in their ground states.d) The peculiarities of the electronic structures of clusters can be deduced from the presence of many “surface” atoms. The theoretical results agree with experimental data presently available and they are useful for interpretation of the experimental findings.     

Theoretical studies of structural and electronic properties of AlnAsn clusters

We present theoretical results of size dependent structural, electronic, and optical properties of ligand‐free stoichiometric Al_nAs_n clusters of zinc‐blende modification. The investigation is done using a simplified parametrized linear combination of atomic orbital–density functional theory‐local density approximation–tight‐binding (LCAO–DFT–LDA–TB) method and consider clusters with n up to around 100. Initial structures have assumed as spherical parts of infinite zinc‐blende structure and then allowed to relax to the closest local‐energy‐minimum structure. We analyze the radial distributions of atoms, Mulliken populations, electronic energy levels (in particular, HOMO and LUMO), bandgap, and stability as a function of size and composition. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Size dependent structural and electronic properties of MgO nanotube clusters

MgO nanotube clusters which cross sections are composed of two‐, three‐, four‐, and five‐membered rings are constructed and studied by the density functional theory at B3LYP/6‐31G(d) level. The variations of bond length present anisotropic effect. Three‐membered ring nanotube cluster is the most stable tube among these MgO isomers. Mixed covalent and ionic bonding always exists in MgO nanotube clusters. With increasing length of MgO nanotube clusters, the averaged atomic charge increases, and converge to 1.227; the s‐p separation of O bands decreases; whereas energy gap nearby frontier orbitals present dramatic difference corresponding to various structure family. It is possible that MgO nanotube clusters show electronic properties of semiconductor. An interpretation for MgO nanotube clusters fabricated by simply thermal methods is proposed. The structural and electronic properties of MgO nanotube clusters are discussed systematically in details. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Thermodynamic properties of small rare gas clusters by path integral Monte Carlo simulations: a preliminary study

A strategy for reducing the risk of non-ergodic simulations in Monte Carlo calculations of the thermodynamic properties of clusters is discussed with the support of some examples. The results obtained attest the significance of the approach for the low-temperature regime, as non-ergodic sampling of potential energy surfaces is a particularly insidious occurrence. Fourier path integral Monte Carlo techniques for taking into account quantum effects are adopted, in conjunction with suitable tricks for improving the procedure reliability. Applications are restricted to Lennard-Jones clusters of rare-gas systems.     

Collective excitations of embedded potassium clusters

The collective surface-plasmon excitation of potassium clusters embedded in different dielectric matrices has been studied within the time-dependent local-density-approximation and the jellium model. The matrix has been taken into account through a static dielectric constant in both the cluster ground state and in the determination of the dynamical susceptibility. We conclude that the change in the residual electron-electron interaction when the cluster is introduced in a matrix is a basic effect for the determination of the static polarizabilities and plasma frequencies. As we increase the surface-plasmon energy is shifted to the red and a tendency to saturation is obtained. The red shift is in good agreement with electron-energy-loss spectroscopy experiments.     

Collective excitations of3He clusters

Collective excitations of³He clusters are studied by treating the cluster as a quantum liquid drop. We have used the Random-Phase Approximation sum rules technique within a Density Functional Formalism. Results forL=2 to 10 surface modes and theL=0 volume mode are presented.     

Velocity map imaging of HBr photodissociation in large rare gas clusters

We have implemented the velocity map imaging technique to study clustering in the pulsed supersonic expansions of hydrogen bromide in helium, argon, and xenon. The expansions are characterized by direct imaging of the beam velocity distributions. We have investigated the cluster generation by means of UV photodissociation and photoionization of HBr molecules. Two distinct features appear in the hydrogen atom photofragment images in the clustering regime: (i) photofragments with near zero kinetic energies and (ii) "hot" photofragments originating from vibrationally excited HBr molecules. The origin of both features is attributed to the fragment caging by the cluster. We discuss the nature of the formed clusters based on the change of the photofragment images with the expansion parameters and on the photoionization mass spectra and conclude that single HBr molecule encompassed with rare gas "snowball" is consistent with the experimental observations.     

Optical properties of fractal clusters of small metallic particles

In this paper we describe a method to calculate the optical properties of deterministic fractal clusters. Our method takes advantage of the fact that deterministic fractals can be constructed by an iterative rule. We calculate first the optical properties of a small cluster that describes one stage in the iteration. The optical properties of this cluster are then assigned to an “effective particle”. A small number of these produce the next stage in the fractal construction. We performed the calculations for metallic particles with dielectric functions described by the hydrodynamic model. Results in the dipolar and quadrupolar approximations for a cluster at the second fractal stage shows the double extinction peak often seen in experimental studies.