Generation of CdS clusters using laser ablation: the role of wavelength and fluence

The formation of cationic clusters in the laser ablation of CdS targets has been investigated as a function of wavelength and fluence by mass spectrometric analysis of the plume. Ablation was carried out at the laser wavelengths of 1064, 532, 355, and 266 nm in order to scan the interaction regimes below and above the energy band gap of the material. In all cases, the mass spectra showed stoichiometric Cd _n S _n ⁺ and nonstoichiometric Cd _n S _n−1⁺, Cd _n S _n+1⁺, and Cd _n S _n+2⁺ clusters up to 4900 amu. Cluster size distributions were well represented by a log-normal function, although larger relative abundance for clusters with n=13, 16, 19, 34 was observed (magic numbers). The laser threshold fluence for cluster observation was strongly dependent on wavelength, ranging from around 16 mJ/cm² at 266 nm to more than 300 mJ/cm² at 532 and 1064 nm. According to the behavior of the detected species as a function of fluence, two distinct families were identified: the “light” family containing S₂⁺ and Cd⁺ and the “heavy” clusterized family grouping Cd₂⁺ and Cd _n S _m ⁺. In terms of fluence, it has been determined that the best ratio for clusterization is achieved close to the threshold of appearance of clusters at all wavelengths. At 1064, 532, and 355 nm, the production of “heavy” cations as a function of fluence showed a maximum, indicating the participation of competitive effects, whereas saturation is observed at 266 nm. In terms of relative production, the contribution of the “heavy” family to the total cation signal was significantly lower for 266 nm than for the longer wavelengths. Irradiation at 355 nm in the fluence region of 200 mJ/cm² has been identified as the optimum for the generation of large clusters in CdS.     

Theory of resonant Raman scattering from low-energy collective excitations of interacting electrons in quantum wires

The Raman spectra of quantum wires in the region of electronic intra-band excitations are investigated using one- and two-band models based on the Luttinger approximation with spin. Structures related to charge and spin density modes are identified, and analyzed with respect to their behavior with photon energy and temperature. It is found that the low-energy peaks in the polarized spectra, close to resonance that are commonly assigned to “single particle excitations”, can be interpreted as the signature of spin density excitations. A broad structure in the resonant depolarized spectrum is predicted above the frequency of the spin density excitations. This is due to simultaneous but independent propagation of spin and charge density modes. The results, when compared with experiment, show, that the electronic collective excitations of quantum wires at low energies are characteristic for a non-Fermi liquid. Received: 25 March 1998 / Accepted: 3 June 1998     

Optical absorption spectra of finite systems from a conserving Bethe-Salpeter equation approach

We present a method for computing optical absorption spectra by means of a Bethe-Salpeter equation approach, which is based on a conserving linear response calculation for electron-hole coherences in the presence of an external electromagnetic field. This procedure allows, in principle, for the determination of the electron-hole correlation function self-consistently with the corresponding single-particle Green function. We analyze the general approach for a “one-shot” calculation of the photoabsorption cross section of finite systems, and discuss the importance of scattering and dephasing contributions in this approach. We apply the method to the closed-shell clusters Na₄, Na⁺₉^{+}_{9} and Na⁺₂₁^{+}_{21}, treating one active electron per Na atom.     

Structures and energetics of carbon bridged C 60 clusters

The structures and energetics of carbon bridged C₆₀ clusters (C ₆₀ ) _n C_m have been studied by simulated annealing technique within the tight-binding molecular-dynamics. The “sp² addition” ball-and-chain dimers exhibit odd-even alternations over the number of chain atoms, with the dimers containing even chain atoms more stable against dissociation than their immediate neighbors containing odd chain atoms. In addition to the usual “sp² addition” dimers, a pentagon-linked C₁₂₁ isomer and a hexagon-linked C₁₂₂ isomer are also found to be stable. Based on our tight-binding calculations, trimers and larger clusters can be simply regarded as being made up of independent or weakly interacting dimers, if the C-C₆₀ joints on a single cage are not too close to each other. Large C₆₀ clusters connected by chains each containing only one or two carbon atoms have similar stability to that of constituent dimers, indicating the possibility to form stable C₆₀-carbon polymers. Received 17 January 2001 and Received in final form 26 February 2001     

Structure and dynamics of cationic van-der-Waals clusters

Ar_nHCl⁺ van-der-Waals clusters for n = 1–13 are investigated with the “minimal diatomics-in-molecules (DIM) model” using ab-initio input data obtained from multi-reference configuration-interaction calculations plus subsequent projection onto valence-bond wavefunctions. The results for the complexes with n = 1–3 are checked against ab-initio calculations at the coupled-cluster (CCSD) level with the same one-electron atomic basis set as for the input data generation (aug-cc-pVTZ from Dunning). In addition to the electronic ground state, the first excited state for the triatomic complex (n = 1) is also studied. The results from the DIM model are shown to be in fair agreement with those from advanced conventional ab-initio calculations, although there are differences in detail. The comparison justifies the extension of the DIM approach to n > 3. Systematic analysis of the local minima of the multi-dimensional potential-energy surfaces (PESs), carried out with the combined method described in part I (Monte-Carlo sampling plus subsequent steepest-descent optimization), reveals simple building-up regularities for the most stable structures (i.e. those corresponding to the global PES minimum) at each n: apart from always having a nearly linear (Ar–H–Cl)⁺ fragment as core, the aggregates show little or no symmetry. Secondary local minima are also determined and their structures interpreted. The PESs for the low-lying excited states reveal a much more complicated topography compared to the Ar_nH⁺ clusters allowing a variety of photo-processes. The energy level sequence of the first five excited electronic states and the stability of the clusters in these states is studied as a function of the cluster size n.     

Deposition of mass-selected cluster ions using a pulsed arc cluster-ion source

A PACIS (pulsed arc cluster-ion source) developed for high average cluster-ion currents is presented. The performance of the PACIS at different operational modes is described, and the suitability for cluster-deposition experiments is discussed in comparison with other cluster-ion sources. Maximum currents of mass-selected cluster ions of 3–6 nA of small Si_n ^- (n=4–10) clusters and 0.3–0.5 nA of large Al_n ^+/- (n=20–70) clusters are achieved. The mass-selected cluster ions are soft-landed on a substrate at residual kinetic energies lower than 1 eV/atom, and the samples are characterized by X-ray photoelectron spectroscopy and scanning tunneling microscopy. First results on the soft landing of “magic” Si₄ ^- clusters on graphite are presented. Received: 30 May 2001 / Accepted: 14 June 2001 / Published online: 2 October 2001     

Melting behavior of large disordered sodium clusters

The melting-like transition in disordered sodium clusters Na₉₂ and Na₁₄₂ is studied by performing density functional constant-energy molecular dynamics simulations. The orbital-free version of the density functional formalism is used. In Na₁₄₂ the atoms are distributed in two distinct shells (surface and inner shells) and this cluster melts in two steps: the first one, at ≈130 K, is characterized by the development of a high intrashell atomic mobility, and the second, homogeneous melting at ≈270 K, involves diffusive motion of all the atoms across the whole cluster volume. On the contrary, the melting of Na₉₂ proceeds smoothly over a very broad temperature interval, without any abrupt change in the thermal or structural indicators. The occurrence of two steps in the melting transition is suggested to be related to the existence of a grouping of the atoms in radial shells, even if those shells present a large degree of internal disorder. It then appears that a cluster can be considered fully amorphous (totally disordered) only when there are no radial regions of low atomic density separating shells. The isomer of Na₉₂ studied here fulfills this criterion and its thermal behavior can be considered as representative of that expected for fully amorphous clusters. Disordered Na₁₄₂, on the other hand, that has a discernible structure of an inner and a surface shell, should be considered as not fully disordered. The thermal behavior of these two clusters is also compared to that of icosahedral (totally ordered) sodium clusters of the same sizes. Received 5 February 2001 and Received in final form 21 May 2001     

Hydrogenated carbon clusters produced by highly charged ion impact on solid

The emission of small (hydrogenated) carbon cluster ions C_nHm ⁺ (n =2-22) upon highly charged Xe^q+ (q =20-44) impact on C₈₄ surfaces is studied by means of time-of-flight secondary ion mass spectrometry. The respective stage of hydrogenation/protonation of a certain carbon cluster ion Cn ⁺ is a strong indication for its geometrical structure. From the cluster ion yield as a function of cluster size it can be concluded, that the hydrogenation takes place after the initial carbon cluster formation. The carbon clusters seem to be emitted as an entity in agreement with “equilibrium” and “shock wave” models. Received 4 February 2000     

A symmetry adapted approach to vibrational excitations in atomic clusters

An algebraic method especially suited to describe the strongly anharmonic vibrational spectra in molecules may be an appropriate framework to study the vibrational spectra of Na _n ⁺ clusters, where nearly flat potential energy surfaces and the appearance of close lying isomers have been reported. As an illustration we describe the model and apply it to the Be₄, H ₃ ⁺ , Be₃ and Na ₃ ⁺ clusters. Presented by A. Frank at the International Conference on “Atomic Nuclei and Metallic Clusters”, Prague, September 1–5, 1997. This work was supported in part by the European Community under contract No. CI1*-CT94-0072, DGAPA-UNAM under project IN101997 and Spanish DGCYT under project PB92-0663.     

Quantum chemical study of electronic and dynamic properties of metal and mixed non-stoichiometric clusters

The aim of this contribution is to show that quantum chemistry has suitable tools to extract the specific properties of small metallic and mixed non-stoichiometric clusters which cannot be obtained by extrapolation from the bulk properties to the atom. For this purpose, first the main features of the methods used for the calculations of the ground and excited states of clusters valid at zero temperature (T=0) will be sketched and the factors determining accuracy of results will be pointed out. The structural and optical response properties of cationic Na _n ⁺ clusters as a function of size will be presented and compared with experimental data. The series of non-stoichiometric alkali-halide clusters containing single and multiple excess electrons will serve as prototypes to study a possible “metal-insulator transition” and “segregation into metallic and ionic parts” in finite systems. Second, an outline of ab initio molecular dynamics methods based on gradient corrected density functional approach with gaussian basis used for determination of temperature dependent ground state properties will be presented. Different temperature behavior of distinct type of structures will be illustrated on an example of Li ₉ ⁺ cluster. Presented by V. Bonačić-Koutecky at the International Conference on “Atomic Nuclei and Metallic Clusters”, Prague, September 1–5, 1997. This work has been supported by the Deutsche Forschungsgemeinschaft (SFB 337, Energy transfer in molecular aggregates) and the Consiglio Nationale delle Ricerche (CNR, Rome).     

Fermi-level engineering of BaTiO3 by alkali codoping: increasing the near-infrared absorption by rhodium

Using electron paramagnetic resonance, optical absorption, and fast spectroscopy of light-induced absorption changes, it is shown that codoping BaTiO₃:Rh with Na_Ba acceptors raises the charge state of Rh³⁺ to Rh⁴⁺. Subsequent oxidation under high oxygen pressures can lower the Fermi level to Rh^4+/5+, leading to increased infrared absorption. The light-induced charge transfer in such specimens is characterised by “one center” behaviour. Received: 18 November 1998 / Revised version: 23 December 1998 / Published online: 7 April 1999     

Structure and dynamics of cationic van-der-Waals clusters

Ar_nHCl⁺ van-der-Waals clusters for n = 1–13 are investigated with the “minimal diatomics-in-molecules (DIM) model” using ab-initio input data obtained from multi-reference configuration-interaction calculations plus subsequent projection onto valence-bond wavefunctions. The results for the complexes with n = 1–3 are checked against ab-initio calculations at the coupled-cluster (CCSD) level with the same one-electron atomic basis set as for the input data generation (aug-cc-pVTZ from Dunning). In addition to the electronic ground state, the first excited ²A^￠^2\!A^{\prime} state for the triatomic complex (n = 1) is also studied. The results from the DIM model are shown to be in fair agreement with those from advanced conventional ab-initio calculations, although there are differences in detail. The comparison justifies the extension of the DIM approach to n > 3. Systematic analysis of the local minima of the multi-dimensional potential-energy surfaces (PESs), carried out with the combined method described in part I (Monte-Carlo sampling plus subsequent steepest-descent optimization), reveals simple building-up regularities for the most stable structures (i.e. those corresponding to the global PES minimum) at each n: apart from always having a nearly linear (Ar–H–Cl)⁺ fragment as core, the aggregates show little or no symmetry. Secondary local minima are also determined and their structures interpreted. The PESs for the low-lying excited states reveal a much more complicated topography compared to the Ar_nH⁺ clusters allowing a variety of photo-processes. The energy level sequence of the first five excited electronic states and the stability of the clusters in these states is studied as a function of the cluster size n.     

Electronic and geometric structure of doped rare-gas clusters: surface, site and size effects studied with luminescence spectroscopy

The electronic and geometric structure of rare gas clusters doped with rare-gas atoms Rg = Xe, Kr or Ar is investigated with fluorescence excitation spectroscopy in the VUV spectral range. Several absorption bands are observed in the region of the first electronic excitations of the impurity atoms, which are related to the lowest spin-orbit split atomic ³P₁ and ¹P₁ states. Due to influence of surrounding atoms of the cluster, the atomic lines are shifted to the blue and broadened (“electronical cage effect”). From the known interaction potentials and the measured spectral shifts the coordination of the impurity atom in Ar_N, Kr_N, Ne_N and He_N could be studied in great detail. In the interior of Kr_N and Ar_N the Xe atoms are located in substitutional sites with 12 nearest neighbours and internuclear distances comparable to that of the host matrix. In Ne_N and He_N the cluster atoms (18 and 22, respectively) arrange themselves around the Xe impurity with a bondlength comparable to that of the heteronuclear dimer. The results confirm that He clusters are liquid while Ne clusters are solid for N≥ 300. Smaller Ne clusters exhibit a liquid like behaviour. When doping is strong, small Rg_m-clusters (Rg = Xe, Kr, Ar, m≤10 ²) are formed in the interior sites of the host cluster made of Ne or He. Specific electronically excited states, assigned to interface excitons are observed. Their absorption bands appear and shift towards lower energy when the cluster size m increases, according to the Frenkel exciton model. The characteristic bulk excitons appear in the spectra, only when the cluster radius exceeds the penetration depth of the interface exciton, which can be considerably larger than that in free Rg_m clusters. This effect is sensitive to electron affinities of the guest and the host cluster.     

Spectroscopy of alkali atoms and molecules attached to liquid He clusters

Large helium clusters, ranging in size from a few hundred to several thousand atoms, are produced in a nozzle expansion. Combining this source with a pick-up scattering cell in which the clusters can be seeded with chromophores allows us to probe the influence of the helium environment on the atoms and molecules attached to the clusters. Using an alkali as chromophore we recorded laser induced fluorescence spectra of Na atoms and molecules attached to helium clusters. Apart from the spectrum of the Na monomer, we have found spectroscopic bands which can unambiguous be assigned to two bound Na atoms. The first of this bands is due to 1^{1 +} (A) 1¹ _g ⁺ (X) excitations of the covalently bound singlet Na₂ molecule while the second is due to 1³ _g ⁺ 1^{3 +} excitations for the van der Waals bound triplet Na₂ dimer. Both bands have been vibrationally resolved. Furthermore we found very large fluorescence intensities in the region 605–635 nm which are likely due to the excitation of a species containing three Na atoms attached to a helium cluster.     

Effects of tunneling coupling on plasmon modes in asymmetric double-quantum-well structures

The collective charge density excitations in asymmetric double-quantum-well (DQW) structures with different tunneling strengths are systematically studied. In particular, the damping properties of the plasmon modes in various tunneling strengths are investigated in detail. It is shown that plasmon modes in asymmetric DQW structures are quite different from those in symmetric DQW systems. In weak tunneling regime, an intra-subband mode ω _- with an acoustic-like dispersion relation which is damped in symmetric DQW structures arises and coexists with the optical-like mode ω ₊ while the inter-subband mode ω ₁₀ is highly damped. With the tunneling strength being increased, the ω ₁₀ branch gradually becomes undamped and emerges out of the (1-0) single-particle continuum, whereas the ω _- branch gradually approaches the (0-0) single-particle continuum. In intermediate coupling regime, these three branches of modes coexist undamped. In strong tunneling regime, ω _- enters the (0-0) single-particle continuum and becomes damped. Consequently, only the ω ₊ and ω ₁₀ modes exist in this regime. Received 10 July 2001 and Received in final form 17 September 2001     

A Colorimetric and Ratiometric Fluorescent Chemosensor for Fluoride Based on Proton Transfer

N-Phenyl-N’-(3-quinolinyl)urea (1) has been developed as a highly selective colorimetric and ratiometric fluorescent chemosensor for fluoride ion based on a proton transfer mechanism. Evidences for the mechanism were provided by UV-vis and fluorescence titration and especially ¹H and ¹⁹F NMR experiments. The sensor gave the largest ratiometric fluorescent response reported so far (R_max/R_min = 2620) to fluoride. Taking H⁺ as the “recovering reagent”, the sensor can be reversibly “used” and “recovered” for several cycles with only a slight decay of the response ability.     

Thermal emission of electrons from highly excited sodium clusters

Positively charged sodium clusters can be easily ionized by a fs laser pulse of relatively low intensity (<10¹⁰ W/cm²), if the laser is in resonance with the plasmon excitation of the cluster. This ionization process was investigated in detail by measuring the kinetic energy distribution of electrons emitted from a size-selected Na₉₃ ⁺ as a function of the fs laser intensity. In all cases pure Boltzmann-like energy distributions were observed. A comparison with statistical theory shows that the emission is a purely thermal process. It is different to normal thermionic emission insofar as the electrons are emitted from a hot electron system which is only weakly coupled to a cold ionic background. The results demonstrate purely statistical behaviour of a small fermionic system even for very high excitation energy. Received: 25 May 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

Supersymmetry for nuclear cluster systems

A supersymmetry scheme is proposed for nuclear cluster systems. The bosonic sector of the superalgebra describes the relative motion of the clusters, while its fermionic sector is associated with their internal structure. An example of core + α configurations is discussed in which the core is a p-shell nucleus and the underlying superalgebra is U(4|12). The α-cluster states of the nuclei ²⁰Ne and ¹⁹F are analyzed and correlations between their spectra, electric quadrupole transitions, and one-nucleon transfer reactions are interpreted in terms of U(4|12) supersymmetry. Received: 14 September 2001 / Accepted: 26 October 2001     

Ion-beam-assisted MBE growth of semi-spherical SiGe/Si nano-structures

Semi-spherical SiGe/Si nano-structures of a new type are presented. Epitaxial islands of 30–40 nm in base diameter and 11 nm in height and having a density of about 6×10¹⁰ cm^-2 were produced on (001) Si by molecular beam epitaxial growth of Si/Si_0.5Ge_0.5 layers with in situ implantation of 1-keV As⁺ ions. It was found by cross-section transmission electron microscopy that the islands have a complicated inner structure and consist of a micro-twin nucleus and semi-spherical nano-layers of various SiGe compositions. The nature of the surface patterning is interpreted by stress relaxation through implantation-induced defects. Received: 12 July 2001 / Accepted: 4 September 2001 / Published online: 2 October 2001     

Medium effects in the production and π0γ decay of ω-mesons in pA collisions in the GeV region

The ω resonance production and its π⁰γ decay in pA reactions close to threshold is considered within the Intranuclear Cascade (INC) model. The π⁰γ invariant-mass distribution shows two components which correspond to the ω decay “inside” and “outside” the nucleus, respectively. The “inside” component is distorted by medium effects, which introduce a mass shift as well as collisional broadening for the ω-meson and its decaying pion. The relative contribution of the “inside” component is analyzed in detail for different kinematical conditions and nuclear targets. It is demonstrated that a measurement of the correlation in azimuthal angle between the π⁰ and γ momenta allows to separate events related to the “inside”ω decay from different sources of background when uncorrelated π⁰'s and γ's are produced. Received: 2 April 2001 / Accepted: 5 June 2001