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.     

Collectivity in the optical response. of small metal clusters

The question of whether the linear absorption spectra of metal clusters can be interpreted as density oscillations (collective “plasmons”) or can only be understood as transitions between distinct molecular states is still a matter of debate for clusters with only a few electrons. We calculate the photo-absorption spectra of Na₂ and Na₅ ⁺ comparing two different methods: quantum fluid dynamics and time-dependent density functional theory. The changes in the electronic structure associated with particular excitations are visualized in “snapshots” via transition densities. Our analysis shows that even for the smallest clusters, the observed excitations can be interpreted as intuitively understandable density oscillations. For Na₅ ⁺, the importance of self-interaction corrections to the adiabatic local density approximation is demonstrated. Received: 1 July 2001 / Published online: 10 October 2001     

Mesoscopic and macroscopic dipole clusters: Structure and phase transitions

A two dimensional (2D) classical system of dipole particles confined by a quadratic potential is studied. This system can be used as a model for rare electrons in semiconductor structures near a metal electrode, indirect excitons in coupled quantum dots etc. For clusters of N ≤ 80 particles ground state configurations and appropriate eigenfrequencies and eigenvectors for the normal modes are found. Monte-Carlo and molecular dynamic methods are used to study the order-disorder transition (the “melting” of clusters). In mesoscopic clusters (N < 37) there is a hierarchy of transitions: at lower temperatures an intershell orientational disordering of pairs of shells takes place; at higher temperatures the intershell diffusion sets in and the shell structure disappears. In “macroscopic” clusters (N > 37) an orientational “melting” of only the outer shell is possible. The most stable clusters (having both maximal lowest nonzero eigenfrequencies and maximal temperatures of total melting) are those of completed crystal shells which are concentric groups of nodes of 2D hexagonal lattice with a number of nodes placed in the center of them. The picture of disordering in clusters is compared with that in an infinite 2D dipole system. The study of the radial diffusion constant, the structure factor, the local minima distribution and other quantities shows that the melting temperature is a nonmonotonic function of the number of particles in the system. The dynamical equilibrium between “solid-like” and “orientationally disordered” forms of clusters is considered.     

Theoretical exploration of ultrafast spectroscopy of small clusters

We present the ultrafast multistate nuclear dynamics involving adiabatic and nonadiabatic excited states of non-stoichiometric halide deficient clusters (Na_nF_n-1) characterized by strong ionic bonding and one-excess electron for which the “frozen ionic bonds” approximation has been justified allowing to consider the optical response of the single excess electron in the effective field of the other electrons. We combined the Wigner-Moyal representation of the vibronic density matrix with the ab initio multi state molecular dynamics in the ground and excited electronic states including the nonadiabatic couplings calculated “on the fly” at low computational demand. This method allows the simulation of femtosecond pump-probe and pump-dump signals based on an analytical formulation, which utilizes temperature dependent ground state initial conditions, an ensemble of trajectories carried out on the electronic excited state as well as on the ground state after the passage through the conical intersection in the case of nonadiabatic dynamics and for probing either in the cationic state or in the ground state. The choice of the systems we presented has been made in order to determine the timescales of the fast geometric relaxation leaving the bonding frame intact as during the dynamics in the first excited state of Na₄F₃, and of the bond breaking processes leading to conical intersection between the first excited state and the ground state as in Na₃F₂. The former is the smallest finite system prototype for an surface F-center of bulk color centers. The latter allows to study the photo isomerization in full complexity taking into account all degrees of freedom. In the case of Na₄F₃ after the fast geometric relaxation in the excited state leading to deformed cuboidal structure without breaking of bonds, different types of internal vibrational redistribution (IVR) processes have been identified in pump-dump signals by tuning the dump laser. In contrast, from the analysis of the pump-probe signals of Na₃F₂ cluster, the timescales for the metallic and the ionic bond breaking, as well as for the passage through conical intersection have been determined. Finally the conditions under which these processes can be experimentally observed have been identified. Received 22 December 2000     

A Characteristic Decay Semigroup for the Resonances of Trace Class Perturbations with Analyticity Conditions of Semibounded Hamiltonians

To asymptotic complete scattering systems {M ₊+V,M ₊} on H₊:=L²(R₊,K{\mathcal{H}}_{+}:=L^{2}(\mathbf{R}_{+},{\mathcal{K}}, d λ), where M ₊ is the multiplication operator on H₊{\mathcal{H}}_{+} and V is a trace class operator with analyticity conditions, a decay semigroup is associated such that the spectrum of the generator of this semigroup coincides with the set of all resonances (poles of the analytic continuation of the scattering matrix into the lower half plane across the positive half line), i.e. the decay semigroup yields a “time-dependent” characterization of the resonances. As a counterpart a “spectral characterization” is mentioned which is due to the “eigenvalue-like” properties of resonances.     

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.     

Thermal hopping ofμ + between “FμF” centres in NaF

Strongly hydrogen-bonded diamagnetic “FμF” centres are formed by theμ ⁺ in a wide variety of fluoride crystals. Hydrogen atoms are expected to form similar “FHF” complexes. Through the “motional narrowing” of the zero-field muon relaxation function in NaF, we have observed an Arrhenius temperature dependence of the dissociation rate of theFμF complex, yielding a binding energy of 1700 (200) K for theμ ⁺ in theFμF centre.     

Formation mechanisms of nanocomposite layers based on multiwalled carbon nanotubes and non-stoichiometric tin oxide

Nanocomposite layers based on multiwalled carbon nanotubes (MWCNTs) and non-stoichiometric tin oxide (SnO _x ) have been grown by magnetron deposition and CVD methods. In the case of the CVD method, the study of the structure and phase composition of obtained nanocomposite layers has shown that a tin oxide “superlattice” is formed in the MWCNT layer volume, fixed by SnO _x islands on the MWCNT surface. During magnetron deposition, the MWCNT surface is uniformly coated with tin oxide islands, which causes a change in properties of individual nanotubes. Electrical measurements have revealed the sensitivity of nanocomposite layers to (NO₂)⁻ molecule adsorption, which is qualitatively explained by a change in the conductivity of the semiconductor fraction of p-type MWCNTs.     

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.     

Two-dimensional mesoscopic dusty plasma clusters: Structure and phase transitions

A two-dimensional mesoscopic cluster of “dusty plasma” particles, which can be interpreted as a system of microparticles in an rf gas discharge, is investigated. The ground-state configurations and corresponding eigenfrequencies and eigenvectors are found for clusters of N=22–40 particles in a harmonic confining potential. It is shown that a change in the Debye screening length R of the particle charge in the plasma can cause structural transformations of the ground state of the system, manifested as first-order or second-order phase transitions with respect to the parameter R. The disorder (“melting”) of the clusters is analyzed in detail by Monte Carlo simulation and molecular dynamics. By varying the characteristic range of particle interaction in a cluster, it is possible to modulate its thermodynamic properties and the character of the phase transitions, thereby causing a controlled transition of the system into the fully ordered, orientationally disordered, or fully disordered state. The possibility of dusty plasma clusters coexisting in different states is discussed. Zh. éksp. Teor. Fiz. 116, 1300–1312 (October 1999)     

μ+SR studies on superconducting YBa2(Cu1−xFex)3Oy system

Spin-glass like magnetic ordering of iron moments was observed in both orthorhombic and tetragonal YBa₂(Cu_1−xFe_x)₃O_y (x=0.08) by μ⁺SR measurements. In a “Tetra” sample, all the muons sense the superconducting transition at 60 K and magnetic ordering at around 15 K, while in an “Ortho” sample they reveal that two magnetically different parts exist in the sample: about 40% of the sample is superconducting withT _c ≈90K and the remaining part is magnetic withT _M≈33K. These phenomena can be explained in terms of clustering of the Fe atoms in the “Ortho” sample.     

Laser photoionization spectroscopy of rare-earth elements: New results on nuclear electromagnetic moments and charge radii of Eu,Gd and Tb isotopes

New results on spins, electromagnetic moments and isotopic changes of nuclear charge radii for ₆₃ ^157–159 Eu, ₆₄ ^{146, 148, 150} Cd and ₆₅ ^{147–155, 157, 159} Tb have been obtained from hyperfine structure and isotope shifte measured with laser resonance photoionization technique. These results complement two-dimensional picture (with respect to H and Z) of the changes of nuclear ground state properties near the “critical” neutron numbers N=88–90 in the vicinity of the “magric” proten number Z=64.     

Investigation of low-temperature quantum diffusion in α-iron byμ + SR experiments on a single-crystal sphereSR experiments on a single-crystal sphere

The longitudinalμ ⁺-spin relaxation rate has been measured on a high-purity spherical α-iron single crystal at temperaturesT down to 20 mK and in applied magnetic fieldsB _appl parallel to 〈111〉 up to 3 T. Only above 1 K can the data be satisfactorily described by one rate constantГ. At 1 T≤B _appl≤2 T and 50 mK≤T≤300 mK, oscillations (“wiggles”) were in addition superimposed on the longitudinal relaxation. A qualitative understanding of the measurements may be achieved in terms of the increasing influence of internal stresses onμ ⁺ diffusion as the temperature is lowered.     

Phase diagram and isotope effect in cobaltites with spin-state transitions

The oxygen isotope effect was investigated in cobalt oxides (Pr_{1 − y} Eu _y )_0.7Ca_0.3CoO₃ (0.12 < y < 0.26). The measurements of magnetization, electric resistivity, differential magnetic susceptibility, thermal expansion, and specific heat show that as the Eu concentration increases, a transition from “ferromagnetic metal” to “weakly magnetic insulator” is observed at y ≈ 0.18. In the insulating ground state, the transition occurs with a Co spin-state change that is suppressed in the ferromagnetic (FM) metallic phase. The spin-state transition at y > 0.18 is accompanied by a substantial oxygen isotope effect that is virtually absent in the FM phase (y < 0.18).     

Stability of muon-oxygen bond sites in RBa2Cu3O7

Relative energies of muon probe sites in the chain region of RBa₂Cu₃O₇ (RBCO) are investigated using a molecular quantum chemistry calculation for (Oμ)⁻ embedded in a cluster of point charges to simulate local charge distributions in RBCO. Partial Cu−O chain covalency results in a O-μ...O muon site between the chain and bridging oxygens. However, Cu-μ “hydride”-like sites are suggested by results for nominally ionic clusters.     

A simple theory of condensation

A simple assumption of the emergence in gas of small atomic clusters consisting of c particles each leads to a phase separation (first-order transition). It reveals itself by the emergence of a “forbidden” density range starting at a certain temperature. Defining this latter value as the critical temperature predicts the existence of an interval with the anomalous heat capacity behavior c _p ∝ ΔT ^−1/c . The value c = 13 suggested in the literature yields the heat capacity exponent α = 0.077.     

The origin of thermal hadron production

Multihadron production in high energy collisions, from e⁺e^- annihilation to heavy ion interactions, shows remarkable thermal behaviour, specified by a universal “Hagedorn” temperature. We argue that this hadronic radiation is formed by tunneling through the event horizon of colour confinement, i.e., that it is the QCD counterpart of Hawking-Unruh radiation from black holes. It is shown to be emitted at a universal temperature T_H ≃ (σ/2 π)^1/2, where σ denotes the string tension. Since the event horizon does not allow information transfer, the radiation is thermal “at birth”.     

Giant magnetoresistance in Hg<Subscript>1−x−y</Subscript>Mn<Subscript>x</Subscript>Fe<Subscript>y</Subscript>Te crystals

Giant magnetoresistance in Hg _1−x−y Mn _x Fe _y Te crystals is caused by clusters with “antiferromagnetic” (Mn-Te-Mn-Te, Mn-Te-Fe-Te) and “ferromagnetic” (Fe-Fe-Fe) ordering. The effect is due to the fact that the charge carriers taking part in electric current interact with the “ferromagnetic” cluster subsystem (Fe-Fe-Fe) magnetized to saturation and become spin-polarized. These spin-polarized charge carriers are strongly scattered by the “antiferromagnetic” Mn-Te-Mn-Te and Mn-Te-Fe-Te clusters, because the magnetic moments inside the clusters and resultant moments of clusters have chaotic orientations. Investigations of kinetic coefficients of Hg _1−x−y Mn _x Fe _y Te crystals before and after thermal treatment show that there is no marked correlation between the giant magnetoresistance and charge-carrier concentration, mobility, and band parameters of crystals. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 28–33, October, 2007.     

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     

Subthreshold ϕ-meson production and medium effects in proton-nucleus reactions

Within the spectral function approach, we study the direct production and decay via the dikaon (dimuon) channel of ϕ mesons in the interactions of 2.4-and 2.7-GeV protons with light and medium target nuclei. It is shown that the K ⁺ K ⁻ (μ⁺ μ⁻) invariant-mass distribution consists of the two components, which correspond to the ϕ decay “outside” and “inside” the target nucleus. The first (narrow) component has the free ϕ width, while the second (broad) component is distorted by the nuclear matter owing to resonance-nucleon scattering and a possible in-medium modification of the kaons and ρ meson at finite baryon density. The relative strength of the “inside” and “outside” components is analyzed in different scenarios for the ϕ width and momentum cut. It is demonstrated that the width of the resulting dimuon invariant-mass distribution on medium nuclei is larger than the free ϕ width by a factor of about 2 if the total ϕ in-medium width is used and the respective cutoff for the ϕ three-momentum is applied, whereas the resulting dikaon invariant-mass distribution has an insignificant sensitivity to the ϕ in-medium properties owing to the strong absorption of the K ⁻ in the surrounding nuclear matter. On the other hand, because of the distortion of the K ⁺ and K ⁻ on their way out of the target nucleus mainly due to the hadronic kaon potentials, the latter distribution is broadened and shifted to higher invariant masses, which means that the measurement of such broadening would give additional evidence for the modification of the kaon and antikaon properties in the nuclear medium. The text was submitted by the author in English.