Ionic structure effects on the optical response of lithium clusters

The optical response of alkali metal clusters is shown to be sensitive to a proper treatment of the electronion interaction and to the ionic spatial structure. A spherical symmetry model based on a combination of a geometrical optimization of the ionic structure and the random phase approximation (RPA) with exact exchange is applied to calculate the optical response of Li ₁₃₉ ⁺ . The optical response obtained within this model is in good agreement with the measured giant dipole resonance.     

Ionization potential measurements of hydrogenated lithium clusters

Ionization Potentials of Li_nH_m clusters have been measured by photoionization. As in Li_n, odd-even alternations and shell closing effects are observed. In a first approximation, we find that Li_nH clusters behave like Li_n–1 and Li_nH₂ like Li_n–2. The results may be interpreted by assuming that the bonding of one hydrogen localizes one electron and that the other electrons remain delocalized.     

Evaporation rates for liquid clusters

An expression for the evaporation rate of neutral atoms from a hot liquid cluster is suggested. It combines Weisskopf's statistical model with a level density that is derived from the experimentally known free energy of a macroscopic droplet of the cluster material. For the case of sodium clusters, it is compared with the rate based on the level density of a system of oscillators. For the same internal energy the latter gives substantially larger evaporation rates, whereas for equal temperature the increase is moderate. For large clusters the electronic contribution to the entropy can no longer be neglected.     

Dynamics of the barium-molecule system within large argon clusters

The effects of adding molecules on the LIF at 540 nm of a barium atom at the surface of an argon cluster (average size 420) has been investigated. We showed that molecules like ethanol,n-hexane and O₂ from stable complexes with ground state barium. In the case of molecules like N₂, CH₄ and SF₆, the collisional quenching of solvated Ba(¹ P) is observed. The large quenching rates obtained are interpreted by a surface mobility of the collisional partners. Moreover, we showed that this collisional quenching leads to the ejection of free Ba(³ P ₁).     

Ionic core effects on the mie resonance in lithium clusters

We investigate the effects of the atomic cores on the Mie resonance in lithium metal clusters, perturbing a jellium Hamiltonian with zero-range pseudopotentials. The resonance is red-shifted with respect to the classical formula by core effects, most important of which is the increased effective mass due to the core potentials. Much of the large shift seen in lithium clusters is thereby explained if the strength of the pseudopotentials is taken from band structure calculations. However, such pseudopotentials cause the resonance to be greatly broadened, contrary to observation.     

Formation and fragmentation of C n + clusters produced from a C60/C70 mixture in an electron-impact ion source

Various fullerene ions are generated in a standard plasma ion source from a vaporized mixture of C₆₀/C₇₀. Except C ₆₀ ⁺ and C ₇₀ ⁺ , the fullerene ions are formed by fragmentation of C₆₀ or C₇₀ excited by electron impact. Information on the structure and stability of the fullerene ions is obtained by studying unimolecular dissociation and collision-induced fragmentation of C ₆₀ ⁺ , C ₅₈ ⁺ and C ₅₆ ⁺ in H₂ and Ar target gases.     

Computer simulations of HREM images of metal clusters

Multislice calculations have been performed for Ag, Pd and Au clusters in the size range of 5.0 nm diameter of cuboctahedral, icosahedral and decahedral structures. It could be shown that tilt series are necessary for the classification of the structures. Particularly for arbitrary orientations, i.e. deviations from main directions such as 2-, 3- and 5-fold axes, the performance of computer simulations is mandatory. The influence of absorption is also studied for the case of a 100 kV microscope by introducing a complex potential.     

Isomerisation and phase transitions in small sodium clusters

Using a distance-dependent tight-binding hamiltonian, we have studied the influence of the temperature on the geometries of small alkali clusters (Na₄, Na₈, and Na₂₀). We have applied a Monte-Carlo thermodynamical method which consists in performing canonical samplings for various temperatures, these samplings being reexpressed in the microcanonical ensemble. This method provides thermodynamical values such as the entropy and the specific heat. Their behaviour shows one phase transition in the case of Na₄ and Na₈, and two phase transitions for Na₂₀. As concerns Na₄ and Na₈, the transition occurs at 200 K, between a solid-like phase and a phase for which the geometry of these clusters oscillates between numerous shapes. In the case of Na₂₀, the two observed phase transitions can be described as a melting of the surface atoms (at 200 K) preliminarily to the fluctuation of an inner icosahedron seed (at 300 K).     

Preparation and study of silver clusters stabilized by matrices of different chemical nature

Small silver clusters characterized by an absorption band (a.b.) at 320–340 nm were stabilized in matrices of different chemical nature. Among them Ag-alumosilicate was a most suitable system for cluster study by different physical and chemical methods. Clusters introduced into the zeolite of mordenite kind were found to be the most stable. Size of stabilized silver clusters measured by different methods is discussed.     

Infrared multiphoton excitation of refractory metal clusters

Photoexcitation and photoionization experiments on small Tungsten and Niobium clusters were performed with a Q-switched Nd:YAG laser (1064 nm) and a reflectron type time-of-flight mass spectrometer. For low laser fluences the monomer and very small clusters do not show up in the mass spectra. Furthermore, the detected cluster ions show very asymmetric peak shapes caused by delayed ionization (thermionic emission). For high photon fluences photoions with up to charge state +3 could be detected.     

Collisional process involving atomic cluster ions

Collision of Ar cluster ions, Ar _n ⁺ (n=3–16), with He and Ne atoms was investigated by use of mass spectroscopic techniques. The cross sections for the production of Ar _n ⁺ (nn) were measured as functions of the size of the parent cluster ion and the collision energy (0.1–10 eV in the center-of-mass frame). These results were analyzed in the scheme of hard-sphere spectator collision with RRK theory. It was concluded that the reaction proceeds via collisional excitation of the parent cluster ion and following sequential loss of the constituent Ar atoms.This paper was originally submitted in connection with the 2nd. Int. Conference on Atomic and Nuclear Clusters held in Santorini from 28. June-2. July 1993 and is published here as a regular article after an independent refereeing procedure according to the standards of Z. Phys. D     

Electronic and geometrical structure of noble metal clusters

We investigate the electronic and structural properties of small (N 20) and medium sized (N 500) clusters of Cu, using the first principles Tight-Binding Linear Muffin-Tin Orbitals (TB-LMTO) method in connection with the real-space recursion scheme. We find the electronic structure resembling the one of simple alkali metal clusters: Pronounced shell closing effects can be identified in the ionization potentials as well as in the HOMO-LUMO gaps for the magic sizesN=8, 20, 34 and 40. The low-energy equilibrium geometries show considerable Jahn-Teller distortions, just as in the case of alkali metals.This article was processed using Springer-Verlag T_EX Z.Physik D macro package 1.0 and the AMS fonts, developed by the American Mathematical Society.     

Exchange effects on electronic states in jellium clusters

Hartree-Fock calculations are done for finite number of valence electrons (8, 20, 40, and 58) in a positively charged uniform background (jellium) with the density of bulk sodium. Differences and similarities with the results of Kohn-Sham local-density calculations are discussed. State-dependence and suppression of the wave functions are the two important effects coming from the nonlocality of the Hartree-Fock potential. These two effects, however, cancel in the density profile of electrons. The Kohn-Sham calculations consequently produce similar density profiles as in the Hartree-Fock calculations. The dipole polarizability is also calculated for 8-mers. The calculated value is still smaller than the measured one and is not an improvement of the insufficient Kohn-Sham result.deceased     

Photoionization of small silicon clusters: ionization potentials for Si2 to Si40

Photoionization thresholds of Si _n (n=2–40) were examined by vacuum UV radiation (5.7–8.5 eV) generated by stimulated Raman scattering of narrow-bandwidth 193-nm radiation in high pressure hydrogen and deuterium gases. A strong threshold energy dependence on cluster size is observed, featuring major maxima at 10 and 20. The magic behavior atn=10 is consistent with the results of the photofragmentation and CID experiments reported previously.     

Effective magnetization of rotating free ferromagnetic metal clusters

The deflection of free magnetic metal clusters in a Stern-Gerlach magnetic field is studied. In particular we investigate magnetic resonance effects resulting from lattice anisotropy and cluster rotation. In analogy to small suspended particles in an oscillating magnetic field the anisotropy field fixed to the rotating atomic lattice of the cluster acts on the cluster magnetization like an rf field in NMR experiments. In our calculation we have used the Bloch equations and assumed different anisotropy field symmetries (uniaxial, cubic). A minimum in the magnetization as a function of the Stern-Gerlach field and also of the cluster size, as observed recently, is obtained under certain conditions. However, such a resonance behavior occurs only if the distribution of the rotation frequency _rot is relatively narrow, while a broad distribution of _rot yields an almost superparamagnetic behavior. In addition, the strength of the anisotropy field and the relaxation time are important variables which determine the magnetic behavior of the clusters.     

Hamiltonian for diabatic molecular states

Hyperradial-adiabatic potential curves for (dt )⁺ molecular ions calculated for states with total three-body angular momentumJ=1 and total parityp=1, i.e. for the abnormal parity ground set, are demonstrated to be exactly diabatic-hyperradial potential curves for (J=1,p=–1) symmetry adiabatic curves. This could be thought of as a formal manifestation of the -doubling effect. The projection operator method of constructing a diabatic Hamiltonian that was suggested earlier can be naturally used in our case, too.     

Ionization potential of clusters in liquids

Time-resolved observations of the fast electron transfer from an electron donor to metal ions adsorbed on metal clusters in solution have shown that a critical size of the cluster is required to make it capable of accepting electrons. The threshold is attributed to a size dependent redox potential of the cluster, increasing with the nuclearity (in contrast with the ionization potential in the gas phase which decreases when n increases): it corresponds to the nuclearity for which the cluster redox potential becomes more positive than the potential of the electron donor acting as a monitor.New data of redox potentials (or IP) of Ag_n clusters (hydroquinone as monitor) and Cu_n cluster (sulfonatopropylviologen anion as monitor) are derived. The influence of n and of the solvation or the ligand is discussed.     

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.     

Comparison of small metal clusters: Ni, Pd, Pt, Cu, Ag, Au

Structures of small clusters of Ni, Pd, Pt, Cu, Ag, and Au with n=2–34 and n=55 atoms are calculated as functions of number of atoms and temperature by the simulated annealing Monte Carlo method using an embedded atom potential.