The influence of O and C doping on the ionization potentials of Li-clusters

The influence of doping of Li-clusters by electronegative O and C atoms on the ionization potentials was investigated. Experimentally, we report ionization potentials for bare Li_n clusters deduced from photoionization efficiency spectra. The values are compared with the results for Li_nO and Li_nC clusters. Observed differences are largely attributed to a quantum size effect caused by the segregated molecular part around the impurity, which changes the electron work function. Theoretically, the Fermi and exchange-correlation energies which enter the work function, are calculated in the frame of the augmented plane wave (APW) method by taking explicitly into account the presence of the molecular core. The other contribution to the work function, the moment of the double layer at the cluster surface, is computed by solving the corresponding Poisson's equation. Received 9 September 1999 and Received in final form 7 February 2000     

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     

Effect of melting on ionization potential of sodium clusters

The effect of melting transition on the ionization potential has been studied for sodium clusters with 40, 55, 142, and 147 atoms, using ab initio and classical molecular dynamics. Classical and ab initio simulations were performed to determine the ionization potential of Na₁₄₂ and Na₁₄₇ for solid, partly melted, and liquid structures. The results reveal no correlation between the vertical ionization potential and the degree of surface disorder, melting, or the total energy of the cluster obtained with the ab initio method. However, in the case of 40 and 55 atom clusters, the ionization potential seems to decrease when the cluster melts. Received 1st November 2002 Published online 24 April 2003 RID="a" ID="a"e-mail: ar@phys.jyu.fi     

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     

Tight-binding study of structural and electronic properties of silver clusters

Tight-binding model is developed to study the structural and electronic properties of silver clusters. The ground state structures of Ag clusters up to 21 atoms are optimized by molecular dynamics-based genetic algorithm. The results on small Ag_n clusters (n = 3-9) are comparable to ab initio calculations. The size dependence of electronic properties such as density of states, s-d band separation, HOMO-LUMO gap, and ionization potentials are discussed. Magic number behavior at Ag₂, Ag₈, Ag₁₄, Ag₁₈, Ag₂₀ is obtained, in agreement with the prediction of electronic ellipsoid shell model. We suggest that both the electronic and geometrical effect play significant role in the coinage metal clusters. Received 7 August 2000     

Predictions of geometrical structures and ionization potentials for small barium clusters Ba

The geometrical structure of ground state Ba_n clusters (n =2-14) has been predicted from various types of calculations including two ab initio approaches used for the smaller sizes namely HF+MP2( n =2-6), DFT (LSDA)( n =2-6, 9) and one model approach HF+pairwise dispersion used for all sizes investigated here. The lowest energy configurations as well as some isomers have been investigated. The sizes n =4, 7 and 13 are predicted to be the relatively more stable ones and they correspond to the three compact structures: the tetrahedron, the pentagonal bipyramid and the icosahedron. The growth behavior from Ba₇ to Ba₁₃ appears to be characterized by the addition of atoms around a pentagonal bipyramid leading to the icosahedral structure of Ba₁₃ which is consistent with the observed size-distribution of barium clusters. Values for vertical ionization potentials calculated for n =2-5 at the CI level are seen to be in quite good agreement with recent measures. Received: 14 May 1997 / Received in final form: 2 February 1998 / Accepted: 27 February 1998     

Photodissociation dynamics of Cl in a xenon cluster

The photodissociation of a chlorine molecule in the environment of a xenon cluster has been studied experimentally using the real time pump and probe technique through the formation of an XeCl reaction product. The photodissociating system is probed in such a way that the movement of a single chlorine atom in the xenon environment is detected. Various Xe_nCl₂ cluster sizes have been investigated leading to the distinction between uncapped, half-capped and doubly capped structures for these clusters. These structures have a profound influence on the photodissociation dynamics. Retrapping of one chlorine atomic fragment and stabilization of the XeCl reaction product is only observed for the half and doubly capped clusters. The experimental work is complemented by classical molecular dynamics calculations to get a full picture of the photodissociation. Received: 17 February 1998 / Received in final form and Accepted: 28 July 1998     

Structures and its evolution of Ba n ( n =2 ∼ 14) clusters

We have studied the atomic structure and the electronic properties of Ba_n clusters by the ab initio molecular dynamics method. We find that a structural transition to the bulk-like structure begins at Ba₉ cluster, and the structures of the clusters are transferred to be icosahedral-like around n = 13. The relatively high stability for Ba₄, Ba₁₀ and Ba₁₃ clusters are observed. Received 1st December 2000     

Charge transfer between alkali cluster ions and atoms in the 1 to 10 keV collisional energy range

The cross-sections for collisional charge transfer between singly charged free clusters M _n ⁺ (M = Li, Na; n=1...50) and atomic targets A (cesium, potassium) have been measured as a function of collisional relative velocity in laboratory energy range 1–10 keV. For each cluster size, the experimental values of the charge transfer cross-section are fitted with an universal parametric curve with two independent parameters and v_m, the maximum cross-section and the corresponding velocity. For small size clusters (), the characteristic parameters show strong variations with the number of atoms in the cluster. Abrupt dips observed for n=10 and n=22 are attributed to electronic properties. Charge transfer patterns observed for various collisional systems present similarities, which appear more sensitive to cluster quantum size effects than to collision energy defects. In their whole, the and v_m parameters show differences in both their size evolution and their absolute values discussed in term of projectile and target electronic structures. Received 13 April 2000 and Received in final form 29 June 2000     

Magnetization of Gd cluster: Anomalous thermal behavior

Theoretical studies of the temperature (T) dependence of magnetization of Gd₁₃ clusters have been carried out within a classical Heisenberg model using Monte-Carlo simulations. It is shown that for a broad range of values of , defined as the ratio between competing ferro and anti-ferro magnetic couplings, the cluster magnetization increases with T in the low T region, as seen in experiment. The clusters are also shown to exhibit a wide distribution of moments at a given T, which broadens significantly with increasing T. It is suggested that this may affect the observed magnetic behavior of magnetic clusters in Stern-Gerlach experiments. Received 29 May 1999 and Received in final form 5 September 1999     

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     

Electronic structure and magnetism in 4d-transition metal clusters

We analyze the stability of magnetic states obtained within the tight-binding model for cubooctahedral (O_h) and icosahedral (I_h) clusters of early 4d (Y, Zr, Nb, Mo, and Tc) transition metals. Several metastable magnetic clusters are identified which suggests the existence of multiple magnetic solutions in realistic systems. A bulk-like parabolic behavior is observed for the binding energy of O_h and I_h clusters as a function of the atomic number along the 4 d-series. The charge transfer on the central atom changes sign, while the average magnetic moments present an oscillatory behavior as a function of the number of d electrons in the cluster. Our results are in agreement with other theoretical calculations. Received: 20 November 1997 / Received in final form: 9 March 1998 / Accepted: 30 March 1998     

Formation of small water cluster anions by attachment of very slow electrons at high resolution

Using a high resolution laser photoelectron attachment method, we have studied the formation of (H ₂ O) _q ^- (q = 2, 6, 7, 11, 15) cluster ions in collisions of slow free electrons (E = 1-80 meV) and Rydberg electrons (n = 12-300) with water clusters. Resonances at zero energy have been observed, the shapes of which are strongly dependent on cluster size. The results are discussed in terms of the formation of metastable negative ions. Received 8 March 1999     

Electron detachment and fragmentation in collisions between 1.25 keV/carbon and clusters and

The destruction cross-section for 22.5 and 50 keV C^1- , for 10 and 50 keV C₈ ^1- and for 50 and 75 keV C₆₀ ^1- clusters in collisions with H₂ has been measured by an attenuation method. The destruction of the cluster anions is dominated by electron detachment rather than fragmentation and is of the order of the geometric cross-section. The cross-sections vary little with bombarding energy. Received: 16 September 1998 / Received in final form: 23 February 1999     

Electronic correlation effects on the properties of an half-filled octahedron cluster in a magnetic field

The present study focuses on electronic correlation effects on magnetic energy, the spin-spin correlation function of an octahedron cluster in the (3↑, 3 ↓) electronic configuration threaded by a magnetic field. Some other spin configurations are also discussed and various field directions are considered. An accurate diagonalisation technique has been used to solve the Hubbard Hamiltonian. A result is analysed on a linear energy stabilisation at low magnetic flux. Moreover, two types of antiferromagnetic transition versus the flux occurring for a correlation term larger than a critical one have been observed, i.e. the likelihood of a charge excitation before the antiferromagnetic transition. Finally, a comparison between the results obtained from the exact diagonalisation and the Gutzwiller method has been carried out, leading to a suggested modification of the Gutzwiller approach in order to improve it. Received 23 June 1999 and Received in final form 28 July 2000     

Combined experimental and theoretical study of small aluminum oxygen clusters

We report a combined experimental and computational investigation of small Al_nO_m species (n ≤20, m ≤ 12), produced in a laser vaporization cluster source. The oxygen content in the clusters was tuned by varying the oxygen concentration in the carrier gas. Ionization energies are bracketed using different ionizing photon energies in the energy range between 5.37 and 7.89 eV. Among the singly doped Al_nO species, Al₃O and Al₁₅O are found to have relatively low ionization energies, which can be related to the magic character of the corresponding cations. Peculiarly low ionization energies also are observed for specific oxygen rich species (m > 1), suggesting the formation of ionically bound subunits. The structures and ionization energies of singly doped Al_nO^0,+ (n = 1 - 7) clusters were determined using density functional theory (B3LYP/6-311+G(d)). Electronic supplementary material Supplementary Online Material     

Local environment and electron correlation effects on the magnetic properties of clusters

The electronic and magnetic properties of clusters are investigated in the framework of the Hubbard model by treating electron correlations effects in a saddle-point slave-boson approximation. The size dependent single-particle spectrum is calculated using a third moment real-space expansion of the local density of states. Results for the magnetic moments, magnetic order, average number of double occupations and hopping renormalizations are given as a function of the local coordination number z, for different representative values of the Coulomb interaction strength U/t and band filling n. Several transitions between paramagnetic, ferromagnetic and antiferromagnetic behaviors are obtained as a function of z. The environment dependence of the magnetic behavior and of the degree of electron delocalization is analyzed. Advantages and limitations of the present approach are discussed. Received: 8 January 1998 / Revised: 22 June 1998 / Accepted: 6 August 1998     

Photodissociation spectroscopy of the chromium trimer ion

The electronic and geometric structures and photodissociation dynamics of the chromium trimer ion, Cr₃ ⁺, were investigated by photodissociation spectroscopy in the photon-energy range from 1.32 to 5.52 eV. The branching fractions of the product ions, Cr⁺ and Cr₂ ⁺, exhibit stepwise changes at the threshold energies for dissociation into Cr⁺+Cr₂, Cr+Cr₂ ⁺, Cr⁺+2Cr, and Cr^*+Cr₂ ⁺. It is noted that Cr₂ ⁺ is produced even above the threshold for atomization; the excess energy is redistributed to produce a fragment atom, Cr^*, in an excited state. The photodissociation action spectrum is well explained by a mixture of simulated spectra for two nearly-degenerate structural isomers identified by density functional calculations: those having a metastable C_2v structure and the most stable structure slightly distorted from the C_2v one. The barrier height between the two isomers which is lower than the zero-point energy suggests that Cr₃ ⁺ has an intrinsically floppy structure.     

Water-silica interaction in clusters

The interaction of water with SiO ₂ is an important problem in geophysics, materials physics, and environmental science. In this paper, we present recent results on studies of H ₂ O-silica clusters from first-principles Born-Oppenheimer molecular dynamics calculations. Bond strength and chemical stability are investigated as a function of cluster size and chemical composition. Both physisorption and chemisorption of water molecules on the clusters are discussed via analysis of energetics. Calculations of clusters are compared with the results from extended surfaces. The validity of clusters as models of surfaces is discussed.