Softlanding and STM imaging of Ag<Subscript> 561</Subscript> clusters on a C<Subscript> 60</Subscript> monolayer

The low energy deposition of silver cluster cations with 561 (±5) atoms on a cold fullerene covered gold surface has been studied both by scanning tunneling microscopy and molecular dynamics simulation. The special properties of the C₆₀/Au(111) surface result in a noticeable fixation of the clusters without a significant change of the cluster shape. Upon heating to room temperature we observe a flattening or shrinking of the cluster samples due to thermal activation. Similar changes were observed also for mass selected Ag clusters with other sizes. For comparison we also studied Ag islands of similar size, grown by low temperature deposition of Ag atoms and subsequent annealing. A completely different behavior is observed with much broader size distributions and a qualitatively different response to annealing.     

Density-functional study of Mo4S6 on Au(111)

The adsorption site and energetics of Mo₄S₆ on the unreconstructed (111) gold surface was determined by density-functional band-structure calculations. Mo₄S₆ adsorbs preferably via three S atoms at Au–Au bridging sites and three Mo atoms at adjacent threefold hollow sites of the Au(111) surface. The perfectly tetrahedral free cluster becomes trigonally distorted upon adsorption, which indicates the presence of attractive Au–S and Au–Mo interactions. The work of separation amounts to 4.2 eV including gradient corrections. Small peak shifts in the density of electronic states indicate electron transfer from Au to S states and from Mo to Au states, such that a Bader analysis yields a neutral cluster. Electron density difference maps, which visualize the electron redistribution between cluster and substrate in the interface region, show that the electron redistribution is confined to the cluster-surface contact region. PACS 61.46.+w; 73.22.-f; 72.20.-v     

Interfacial properties of Ce<Subscript>0.75</Subscript>Zr<Subscript>0.25</Subscript>O<Subscript>2</Subscript> supported noble metals (Pd,Pt) from first principles

First-principles electronic structure calculations of noble metals (NM=Pd, Pt)/Ce_0.75Zr_0.25O₂ systems are presented. It is found that: the NM adatoms do not prefer to stay at the atop or the bridge sites of the cations (Ce and Zr), but prefer to be adsorbed at or around the anion sites. The most preferable adsorption sites for both the Pd and Pt adatoms are the O-bridge sites neighboring the Zr dopant. The Pt adatom show much stronger interaction with the Ce_0.75Zr_0.25O₂(111) surface than does the Pd adatom. The interactions of the NM/Ce_0.75Zr_0.25O₂(111) interfaces are stronger than those of the corresponding NM/ceria(111) interfaces. There are some metal induced gap states (MIGS) appeared in the gaps of the NM/Ce_0.75Zr_0.25O₂(111) interfaces, which are important to catalytic properties of the NM/Ce_0.75Zr_0.25O₂(111) catalysts.     

Deposition of Ni<Subscript> 13</Subscript> and Cu<Subscript> 13</Subscript> clusters on Ni(111) and Cu(111) surfaces

The soft deposition of Ni₁₃ and Cu₁₃ clusters on Ni(111) and Cu(111) surfaces is studied by means of constant-energy molecular-dynamics simulations. The atomic interactions are described by the Embedded Atom Method. It is shown that the shape of the nickel clusters deposited on Cu(111) surfaces remains rather intact, while the copper clusters impacting on Ni(111) surfaces collapse forming double and triple layered products. Furthermore, it is found that for an impact energy of 0.5 eV/atom the structures of all investigated clusters show the lowest similarity to the original structures, except for the case of nickel clusters deposited on a Cu(111) surface. Finally, it is demonstrated that when cluster and substrate are of different materials, it is possible to control whether the deposition results in largely intact clusters on the substrate or in a spreading of the clusters. This separation into hard and soft clusters can be related to the relative cohesive energy of the crystalline materials.     

Molecular adsorption of NO on free-standing and on graphene-supported Mo<Subscript>3</Subscript>W<Subscript>5</Subscript> cluster: a density functional theory investigation

The adsorption of molecular NO on the free-standing and graphene-supported Mo₃W₅ cluster is studied using methods from the gradient-corrected density functional theory. Before, the effect of the graphene support on the properties of the metal cluster was investigated. The interaction between the metal cluster and the graphene sheet takes place mainly through W atoms, which form up to three bonds with the support. Interaction energies are in the range from 0.6 to 1.5 eV. An amount of charge of about 0.4–0.5 e\(^-\) is transferred from the cluster to the support. Geometric distortions in the metal aggregate are negligible. An important decrease in the magnetic moment of Mo₃W₅ with respect to its free-standing value is observed after the interaction with the support. Molecular NO adsorbs on sites involving W atoms only, both for the free-standing and the supported metal cluster. Adsorption energies are in a range from 2 to 4 eV. A parallel mode is the preferred mode from an energetic point of view. Moreover, for that parallel adsorption mode, the N–O bond is more effectively activated. Magnetic moments change largely after adsorption indicating important rearrangement in the electronic configuration of the metal cluster. An important amount of electronic charge is transferred both from the free-standing and from the supported metal cluster to NO. The amount of charge transferred seems to be closely related to the activation of the N–O bond. The effect of the graphene sheet on the catalytic properties of Mo₃W₅ seems to be negligible, with the exception of some changes in the electronic configuration of the cluster.     

Structures and stability of Al<Subscript><Emphasis Type="Bold">7</Emphasis></Subscript>C and Al<Subscript><Emphasis Type="Bold">7</Emphasis></Subscript>N clusters

We report results of the atomic and electronic structures of Al₇C cluster using ab initio molecular dynamics with ultrasoft pseudopotentials and generalized gradient approximation. The lowest energy structure is found to be the one in which carbon atom occupies an interstitial position in Al₇ cluster. The electronic structure shows that the recent observation [Chem. Phys. Lett. 316, 31 (2000)] of magic behavior of Al₇C^- cluster is due to a large highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) gap which makes Al₇C^- chemically inert. These results have further led us to the finding of a new neutral magic cluster Al₇N which has the same number of valence electrons as in Al₇C^- and a large HOMO-LUMO gap of 1.99 eV. Further, calculations have been carried out on (Al₇N)₂ to study interaction between magic clusters. Received 28 July 2001     

DFT study of BaTiO<Subscript>3</Subscript> (001) surface with O and O<Subscript>2</Subscript> adsorption

Progress of scanning tunneling microscopy (STM) allowed to handle various molecules adsorbed on a given surface. New concepts emerged with molecules on surfaces considered as nano machines by themselves. In this context, a thorough knowledge of surfaces and adsorbed molecules at an atomic scale is thus particularly invaluable. In this work, within the framework of density functional theory (DFT), we present an electronic and structural ab initio study of a BaTiO₃ (001) surface (perovskite structure) in its paraelectric phase. As far as we know the atomic and molecular adsorption of oxygen at surface is then analyzed for the first time in the literature. Relaxation is taken into account for several layers. Its analysis for a depth of at least four layers enables us to conclude that a reasonable approximation for a BaTiO₃ (001) surface is provided with a slab made up of nine plans. The relative stability of two possible terminations is considered. By using a kinetic energy cut off of 400 eV, we found that a surface with BaO termination is more stable than with TiO₂ termination. Consequently, a surface with BaO termination was chosen to adsorb either O atom or O₂ molecule and the corresponding calculations were performed with a coverage 1 on a (1×1) cell. A series of cases with O₂ molecule adsorbed in various geometrical configurations are also analyzed. For O₂, the most favorable adsorption is obtained when the molecule is placed horizontally, with its axis, directed along the Ba-Ba axis and with its centre of gravity located above a Ba atom. The corresponding value of the adsorption energy is -9.70 eV per molecule (-4.85 eV per O atom). The molecule is then rather extended since the O–O distance measures 1.829 ?. By comparison, the adsorption energy of an O atom directly located above a Ba atom is only -3.50 eV. Therefore we are allowed to conclude that the O–O interaction stabilizes atomic adsorption. Also the local densities of states (LDOS) corresponding to various situations are discussed in the present paper. Up to now, we are not aware of experimental data to be compared to our calculated results.     

Polymerization of solid C<Subscript>60</Subscript> under C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> cluster ion bombardment

The structure transformation occurring in fullerene film under bombardment by 50 keV C₆₀⁺ cluster ions is reported. The Raman spectra of the irradiated C₆₀ films reveal a new peak rising at 1458 cm⁻¹ with an increase in the ion fluence. This feature of the Raman spectra suggests linear polymerization of solid C₆₀ induced by the cluster ion impacts. The aligned C₆₀ polymeric chains composing about 5–10 fullerene molecules have been distinguished on the film surface after the high-fluence irradiation using atomic force microscopy (AFM). The surface profiling analysis of the irradiated films has revealed pronounced sputtering during the treatment. The obtained results indicate that the C₆₀ polymerization occurs in a deep layer situated more than 40 nm below the film surface. The deep location of the C₆₀ polymeric phase indirectly confirms the dominant role of shock waves in the detected C₆₀ phase transformation.     

O<Subscript>2</Subscript> photodesorption from a Ag<Subscript>8</Subscript>O<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack> cluster

The decay path of an Ag₈(O₂)^- cluster photoexcited by a 3.1 eV photon is elucidated using time-resolved photoelectron spectroscopy. Photoabsorption results in the formation of an excited state giving rise to a peak in the photoelectron spectra with well-resolved vibrational finestructure. With a lifetime of about 100 fs this bound state decays into an anti-bonding state which dissociates into O₂ and Ag₈^- on a timescale of 10 ps. In the photoelectron spectra, this corresponds to a broad maximum shifting gradually towards higher binding energy while the O₂ and Ag₈^- separate. Finally, the spectrum of bare Ag₈^- appears. This process is unique to small clusters, because on metal surfaces excited state lifetimes are too short to allow for direct dissociation.     

The characteristics for H<Subscript> 2</Subscript><Superscript> +</Superscript>-like impurities confined by spherical quantum dots

The energy spectra of H₂ ⁺-like impurities confined in finite spherical quantum dots have been calculated as a function of the distance between nuclear with different sizes on the basis of effective-mass approximation by linear variational method. B-splines have been used as basis functions, which can easily construct the trial wavefunctions with appropriate boundary and cusp conditions. The quantitative analyses of the partial wave weights for ground state and some low lying states have been done.     

Synthesis of ZnAl<Subscript>2</Subscript>O<Subscript>4</Subscript>/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> complex substrates and growth of GaN films

With the solid phase reaction between pulsed-laser-deposited (PLD) ZnO film and α-Al₂O₃ substrate, ZnAl₂O₄/α-Al₂O₃ complex substrates were synthesized. X-ray diffraction (XRD) spectra show that as the reaction proceeds, ZnAl₂O₄ changes from the initial (111)-oriented single crystal to poly-crystal, and then to inadequate (111) orientation. Corresponding scanning electron microscope (SEM) images indicate that the surface morphology of ZnAl₂O₄ transforms from uniform islands to stick structures, and then to bulgy-line structures. In addition, XRD spectra present that ZnAl₂O₄ prepared at low temperature is unstable at the environment of higher temperature. On the as-obtained ZnAl₂O₄/α-Al₂O₃ substrates, GaN films were grown without any nitride buffer using light-radiation heating low-pressure MOCVD (LRH-LP-MOCVD). XRD spectra indicate that GaN film on this kind of complex substrate changes fromc-axis single crystal to poly-crystal as ZnAl₂O₄ layer is thickened. For the single crystal GaN, its full width at half maximum (FWHM) of X-ray rocking curve is 0.4°. Results indicate that islands on thin ZnAl₂O₄ layer can promote nucleation at initial stage of GaN growth, which leads to the (0001)-oriented GaN film.     

Quantum dynamics of the dissociation of H<Subscript>2</Subscript> on Rh(111)

The dissociative adsorption of H₂ on Rh(111) has been studied by high-dimensional quantum calculations using a coupled channel scheme. The potential energy surface was derived from ab initio total energy calculations using density functional theory together with the generalized gradient approximation to describe exchange-correlation effects. Experimentally, at high kinetic energy a step in the dissociative adsorption probability as a function of kinetic energy has been observed [M. Beutl et al., Surf. Sci. 429, 71 (1999)] which has been attributed to the opening up of a new adsorption channel. This feature in the dissociation probability is reproduced in the calculations for H₂ molecules initially in the ro-vibrational ground state but it is not related to the opening up of an additional dissociation channel. Instead, it is caused by purely dynamical effects. In addition, rotational effects in the H₂ dissociation are addressed.     

Mass-selected Ag<Subscript>3</Subscript> clusters soft-landed onto MgO/Mo(100): femtosecond photoemission and first-principles simulations

The electronic structure of supported mass-selected Ag₃ clusters is analyzed by joint femtosecond photoemission spectroscopy and ab initio theoretical investigations. A wide band gap insulating magnesia ultra-thin film on Mo(100) has been chosen as substrate in order to minimize the electronic interaction between metal clusters and support. After magnesia ultra-thin film preparation no photoemission from the molybdenum substrate is observed anymore, instead very weak two photon photoemission is detected possibly originating from surface or subsurface oxide defect states. Soft-landing deposition of 2 of atomic monolayer equivalents of Ag₃ clusters results in the disappearance also of the MgO two photon photoemission signal, while a strong single photon photoemission signal is detected from states located directly below the Fermi level. The theoretical study of structural, electronic and optical properties of Ag₃ at two model sites of MgO (100), the stoichiometric MgO(100) and an F_S-center defect, based on the DFT method and the embedded cluster model provides insight into the interactions between the cluster and the support which are responsible for the characteristic spectroscopic features.     

Study on the spin-states of cobalt-based double-layer perovskite Sr<Subscript>2</Subscript>Y<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>Co<Subscript>2</Subscript>O<Subscript>7</Subscript>

The spin-states of cobalt based perovskite compounds depend sensitively on the valence state and local crystal environment of Co ions and the rich physical properties arise from strong coupling among charge, spin, and orbital degrees of freedom. While extensive studies have been carried out in the past, most of them concentrated on the isotropic compound LaCoO₃. In this paper, using the unrestricted Hartree-Fock approximation and the real-space recursion method, we have investigated the competition of various magnetically ordered spin-states of anisotropic double-layered perovskite Sr₂Y_0.5Ca_0.5Co₂O₇. The energy comparison among these states shows that the nearest-neighbor high-spin-intermediate-spin ferromagnetically ordered state is the relevant magnetic ground state of the compound. The magnetic structure and sizes of magnetic moments are consistent with the recent experimental observation.     

Experimental evidence for molecular ultrafast dissociation in O<Subscript>2</Subscript> clusters

Resonant Auger spectra of O₂ clusters excited at the O1s edge are reported. After excitation to the repulsive 1s^-13σ^* state, the resulting resonant Auger spectrum displays features that remain constant in kinetic energy as the photon energy is detuned. The shift between known atomic fragment features and these features is consistent with that observed for atoms and clusters in singly charged states in direct photoemission. These findings are strong evidence for the existence of molecular ultrafast dissociation processes within the clusters or on their surface.     

Energy level alignment at interfaces between organic semiconductors and clean ferromagnetic La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> thin film contacts for spin injection

We have studied the energy level alignment at interfaces between clean ferromagnetic La_0.7Sr_0.3MnO₃ and two archetype organic semiconductors, α-sexithiophene and copper-phthalocyanine, by combined X-ray and ultraviolet photoelectron spectroscopy. We observe the formation of a large interface dipole at both studied interfaces and small hole injection barriers. In addition, our results indicate a small chemical interaction between the organic materials and the La_0.7Sr_0.3MnO₃ surface which leads to a pinning of the Fermi level and the relatively small hole injection barriers.     

Improvement of the intergranular pinning energy in uniaxially compacting (Bi-Pb)<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+δ</Subscript> ceramic samples

Measurements of the electrical resistivity as a function of temperature, ρ(T), for different values of applied magnetic field, B_a (0 ≤ B_a ≤ 50 mT), were performed in polycrystalline samples of Bi_1.65Pb_0.35Sr₂Ca₂ Cu₃O_10+δ subjected to different uniaxial compacting pressure (UCP). We have found appreciable differences in the grain orientation between samples by using X-ray diffractometry. From the X-ray diffraction patterns performed, in powder and pellet samples, we have estimated the Lotgering factor along the (00l) direction, F_(00l). The results indicate that F_(00l) increases ~23% with increasing UCP suggesting that grains of these samples are preferentially aligned along the c-axis, which is parallel to the compacting direction. The resistive transition of the samples have been interpreted in terms of the thermally activated flux-creep model. In addition, the effective intergranular pinning energy, U₀, have been determined for different applied magnetic field. The magnetic field dependence of U₀, for B_a > 8 mT, was found to follow a H^{- α} dependence with α = 0.5 for all samples. The analysis of the experimental data strongly suggested that increasing UCP results in appreciable changes in both the grain alignment and the grain connectivity of the samples. We have successfully interpreted the data by considering the existence of three different superconducting levels within the samples: the superconducting grains, the weak-links, and the superconducting clusters.     

Charge dynamics of the spin-density-wave state in BaFe<Subscript>2</Subscript>As<Subscript>2</Subscript>

We report on a thorough optical investigation of BaFe₂As₂ over a broad spectral range and as a function of temperature, focusing our attention on its spin-density-wave (SDW) phase transition at T_SDW = 135 K. While BaFe₂As₂ remains metallic at all temperatures, we observe a depletion in the far infrared energy interval of the optical conductivity below T_SDW, ascribed to the formation of a pseudogap-like feature in the excitation spectrum. This is accompanied by the narrowing of the Drude term consistent with the dc transport results and suggestive of suppression of scattering channels in the SDW state. About 20% of the spectral weight in the far infrared energy interval is affected by the SDW phase transition.     

Simulation of desorption of gold nanoclusters deposited on the (111) surface of Al and Au under bombardment with Au<Subscript>1</Subscript> ions and Au<Subscript>400</Subscript> clusters using the classical molecular dynamics method

The mechanisms of desorption of gold nanoclusters deposited on à substrate under low-energy bombardment with ions and clusters (in the mode of elastic stopping predominance) are analyzed. The classical molecular dynamics method is employed for computer simulation of both “direct” and “indirect” impact of bombarding particles (that is, when a projectile particle either directly interacts with the deposited cluster or penetrates into the substrate without hitting the cluster). Au₁ ions and Au₄₀₀ clusters with an energy of 38 keV and 0.18 keV/atom, respectively, are used as projectile particles. The spherical Au₆₀₅₁ gold nanocluster deposited on a substrate of Al(111) or Au(111) is applied as a target. It is shown that indirect impact does not lead to desorption of the nanocluster from the Al substrate in all considered cases; however, it can initiate desorption from the Au substrate. This phenomenon is quite efficient when the heat spike appearing upon penetration of a projectile particle involves the region of contact between the substrate and the nanocluster deposited on it. As this takes place, an intense flow of the sputtered substrate material transfers a sufficient-for-ejection momentum to the deposited nanocluster.     

Metastable helium cluster He<Stack><Subscript>4</Subscript><Superscript>*</Superscript></Stack>

The existence of a metastable cluster He ₄ ^* with total spin S = 2 is predicted. The cluster consists of two covalently bound excited spin-polarized triplet He ₂ ^* molecules and is rectangular in shape. The electron wavefunctions, the dependence of the energy He ₄ ^* system on the distance between the He ₂ ^* triplet molecules, the atomic spacing, the frequency spectrum of natural oscillations of the cluster, and other characteristics are calculated from first principles. It is shown that the metastable state is formed if one of the excited He ₂ ^* molecules is in the ³Σ _u ⁺ state, while the other is in the ³Π_g state. The radiation lifetime τ of the metastable cluster He ₄ ^* is calculated; it is found to range from 100 to 200 s, which is much longer than the lifetime τ ≈ 20 s of the triplet molecule He ₂ ^* (³Σ _u ⁺ ). The height U ≈ 0.5 eV of the potential barrier preventing the departure from the local energy minimum is determined. The energy E_acc ≈ 9 eV/atom accumulated in the He ₄ ^* cluster is calculated; this energy considerably exceeds the energy of known chemical energy carriers. It is shown that the accumulated energy is released virtually completely during decomposition of the He ₄ ^* cluster into individual helium atoms. This means that helium clusters are a promising material with a high accumulated energy density (HEDM).