Interaction of Cu cluster anions (Cu<Superscript>-</Superscript><Subscript>n</Subscript>, n = 8–11) with oxygen

The reaction of oxygen with Cu cluster anions consisting of 6–11 atoms was studied by means of Time-of-Flight mass (TOF) spectroscopy and Ultraviolet Photoelectron Spectroscopy (UPS). Using molecular oxygen, we found that a Cu^-_n cluster (n=6-11) can react only with one single oxygen molecule, which adsorbs molecularly, implying that the clusters studied here are less reactive towards oxygen chemisorption compared to the smaller clusters (n<5). This result indicates that chemical properties can alter significantly with increasing cluster size. Depending on the cluster source conditions, different cluster structures and reactivity patterns were found. These results are used to qualitatively describe the chemisorption energetics of oxygen on Cu cluster anions.     

Effect of oxygen content and charge on the structure,stability and optoelectronic properties of yttrium oxide clusters

The electronic and geometrical structures of neutral and charged YOn (n=2–12) clusters have been investigated using density functional theory (DFT) with generalized gradient approximation. The oxygen atom in YOn has been found to be in oxo, peroxo and in superoxo forms. The geometrical structures and topologies of small size anionic clusters resemble that of neutral clusters. Yttrium showed higher coordination number than scandium. Computed results reveal the existence of YO₁₀ cluster to have a penta-peroxo oxygen with a homoleptic Y(η² –O₂)₅ geometrical configuration. The HOMO–LUMO gaps decrease with increasing n due to the increase in 2p orbital population of oxygen atoms. It has been shown that in these clusters bonding are predominantly ionic in nature and anions are thermodynamically more stable, due to the charge delocalization between the metal atom and oxygen ligands. YO₁₀⁺ and YO₁₂⁺ were found to be highly exothermic to release one and two oxygen molecules, while YO₁₁⁺ dissociates though the ozonide dissociation channel. Computed absorption spectra of small clusters are mainly contributed by yttrium metal d and s valence orbitals. The absorbance spectra, shifts towards lower energy with cluster size increase, while charge has no substantial effect on the absorption spectrum.     

Charging and stabilization of Pd atoms and clusters on an electron-rich MgO surface

We report density functional theory calculations on the interaction of Pd atoms and small Pd clusters with an electron-rich MgO surface. This surface can be generated by forming a specific kind of defects, named (H⁺)(e⁻) centers, using well known chemical recipes. By deposition of gas-phase Pd atoms on the properly functionalized MgO surface, one can generate collections of small Pd cluster anions with peculiar chemical properties. The (H⁺)(e⁻) centers act as nucleation sites for diffusing Pd atoms and favor the formation of small, thermally stable clusters. The presence of an extra charge on the metal cluster results in a large vibrational red-shift of adsorbed CO molecules. The present results intend to stimulate experimental work to produce stable metal cluster anions on the surface of an ionic oxide.     

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.     

Size-dependent oxidation of Pdn (n 13) on alumina/NiAl(110): Correlation with Pd core level binding energies

Small Pd clusters Pd_n (n = 1, 4, 7, 10, 13) deposited on alumina/NiAl(110) at room temperature were examined by X-ray photoelectron spectroscopy (XPS), as-deposited and after exposure to O₂ at temperatures ranging from 100 to 500 K. After O₂ exposure at 100 K, the Pd clusters showed XPS shifts indicative of oxidation. The exception was Pd₄, which did not oxidize under any conditions. The inertness of Pd₄/alumina/NiAl(110) appears to be correlated with a significantly higher-than-expected Pd 3d binding energy, which we attribute to a particularly stable valence shell. None of the clusters examined oxidized during O₂ exposures at 300 K or above, but He⁺ scattering showed that oxygen was bound on the cluster surfaces. Upon heating, all the oxygen associated with these small clusters appeared to spill over and react with the alumina/NiAl(110) support.     

Application of129Xe NMR spectroscopy and EXAFS to probe the formation of a bimetallic cluster in zeolite Y

Palladium was supported on CaY zeolite by ion exchange of Pd(NH₃) ₄ ²⁺ into CaY zeolite, calcination in O₂ and subsequent reduction with H₂. Platinum and silver were added to this Pd/CaY zeolite by ion exchange of Pt(NH₃) ₄ ²⁺ and Ag⁺, respectively, and subsequent reduction with Hg. Extended X-ray absorption fine structure of these metals indicates that the successive metal-loading treatments lead first to the formation of a 1-nm Pd cluster inside the supercage of CaY zeolite and to the subsequent formation of bimetallic clusters through incorporation of Pt and Ag atoms into the small Pd cluster. The line width and chemical shift of¹²⁹Xe NMR spectrum of xenon gas adsorbed on the zeolite show dramatic changes during the metal clustering procedure, which indicates that¹²⁹Xe NMR spectroscopy can be used to probe the formation of bimetallic clusters.     

Size-dependent oxidation of Pdn (n ? 13) on alumina/NiAl(110): Correlation with Pd core level binding energies

Small Pd clusters Pd_n (n = 1, 4, 7, 10, 13) deposited on alumina/NiAl(110) at room temperature were examined by X-ray photoelectron spectroscopy (XPS), as-deposited and after exposure to O₂ at temperatures ranging from 100 to 500 K. After O₂ exposure at 100 K, the Pd clusters showed XPS shifts indicative of oxidation. The exception was Pd₄, which did not oxidize under any conditions. The inertness of Pd₄/alumina/NiAl(110) appears to be correlated with a significantly higher-than-expected Pd 3d binding energy, which we attribute to a particularly stable valence shell. None of the clusters examined oxidized during O₂ exposures at 300 K or above, but He⁺ scattering showed that oxygen was bound on the cluster surfaces. Upon heating, all the oxygen associated with these small clusters appeared to spill over and react with the alumina/NiAl(110) support.     

Multiply charged titanium cluster anions: production and photodetachment

Titanium clusters are produced by laser vaporization of a metal wire in a helium gas pulse, stored in a Penning trap, size selected and transformed into multiply charged anions by electron attachment. Both doubly and triply charged titanium clusters are observed. For the first observation of photodetachment of electrons from metal cluster dianions, Ti ₅₅ ^2- clusters are selected and excited by a laser pulse, which leads to the emission of an excess electron: Ti ₅₅ ^2- → e⁻ + Ti ₅₅ ^- . This revised version was published online in August 2006 with corrections to the Cover Date.     

Pulsed reactive crossed beam laser ablation of La0.6Ca0.4CoO3 using O: Where does the oxygen come from?

The composition of thin perovskite films, especially the oxygen content, is a crucial parameter which influences many physical properties, such as conductivity and catalytic activity. Films produced by pulsed laser deposition are normally annealed in an oxygen atmosphere after deposition to achieve a desired oxygen content. In pulsed reactive crossed beam laser ablation, no annealing step is necessary, but a fundamental question regarding this deposition technique is still open: where does the oxygen in the films come from?There are three possibilities, i.e. from the target, from the gas background, or from the gas pulse. To answer this question two experiments were performed: ¹⁸O₂ was used during the deposition process as background gas with ¹⁶O anions in the target and ¹⁶O₂ gas pulse, and a ¹⁸O₂ gas pulse with ¹⁶O from the target and background. These experiments revealed that the quantification of the oxygen origin is only possible, when no oxygen exchange occurs at the deposition temperature. The films are characterized after deposition by elastic recoil detection analysis (ERDA) to determine the ¹⁶O/¹⁸O ratio. Experiments with different oxidizing species in the gas pulse (N₂O and O₂) confirm that the oxidizing potential (N₂O > O₂) as well as the number of molecules are important.     

Theoretical investigation of the interaction between the hydrogen atom and Pd clusters

The chemisorption of hydrogen on small Pd_n clusters (n = 1–3) has been investigated using the pseudopotential procedure followed by configuration interaction (PP-CI). The interaction of H with the cluster modeling the three-fold hollow site of the Pd(111) surface is found to be stronger than that at the bridge and the top site models. When H occupies a top site the bonding has a partial ionic character as a consequence of charge transfer from the metal to H. At the bridge and hollow sites the bonding is essentially covalent. The MO energy spectrum of the Pd₃-H (hollow) cluster is characterized by the presence of a well separated MO level ～ 7 eV below the Fermi level which is consistent with the experimentally observed photoelectron spectra of H on Pd(111) surface. The bonding between H and Pd clusters occurs mainly via d-orbitals and seems to be of quite local nature.     

Experimental and Theoretical Study of Hydrogen Atom Abstraction from C2H6 and C4H10 by Zirconium Oxide Clusters Anions

使用配有团簇产生和化学反应源的飞行时间质谱装置,研究了锆氧阴离子团簇Zr_xOy^-与乙烷和丁烷的反应. 在反应中发现了Zr₂O₅H^-和Zr₃O₇H^-产物. 用密度泛函理论研究了乙烷在Zr₂O₅^-上的反应通道,发现乙烷脱氢反应可以发生,从而证明观察到的产物是源于脱氢反应. 该工作揭示了锆氧负离子团簇与烷烃反应中的新通道.     

Ab initio calculation of the geometric,electronic and magnetic properties of neutral and anionic Au n Pd (n = 1–9) clusters

The ab initio method based on density functional theory at the B3PW91 level has been applied to study the geometric, electronic, and magnetic properties of neutral and anionic Au _n Pd (n?=?1–9) clusters. The results show that the most stable geometric structures adopt a three-dimensional structure for neutral Au₇Pd and Au₈Pd clusters, but for anionic clusters, no three-dimensional lowest-energy structures were obtained. The relative stabilities of neutral and anionic Au _n Pd clusters were analysed by means of the dependent relationships between the binding energies per atom, the dissociation energies, the second-order difference of energies, the HOMO–LUMO energy gaps and the cluster size n, and a local odd–even alternation phenomenon was found. Natural population analysis indicates the sequential transfer from the Pd atom to the Au _n frame in Au_1,2,3,5Pd and Au_2,3Pd^? clusters, and from the Au _n frame to the Pd atom in other clusters. Much to our surprise, irrespective of whether it is the total magnetic moment or the local magnetic moment, the magnetic moment presents an odd–even alternation phenomenon as a function of the cluster size n. The magnetic effects are mainly localized on the various atoms (Au or Pd) for different cluster size n.     

A method for measuring the proportion of different plane orientations in metal supported catalysts by gas chemisorption

A method is presented, which allows us to calculate the percentage of metal surface atoms with different coordination numbers, on metal supported catalysts. This method is based on gas-metal stoichiometry values reported for the chemisorption of H₂, O₂ and CO on well defined monocrystals, and on gas chemisorption measurements on metal supported catalysts. It has here been applied to a series of Pd/SiO₂ catalysts.     

Comparison of the interaction of Pd with positively and negatively poled LiNbO3(0 0 0 1)

To investigate the possibility of manipulating the surface chemical properties of finely dispersed metal films through ferroelectric polarization, the interaction of palladium with oppositely poled LiNbO₃(0 0 0 1) substrates was characterized. Low energy ion scattering indicated that the Pd tended to form three-dimensional clusters on both positively and negatively poled substrates even at the lowest coverages. X-ray photoelectron spectroscopy (XPS) showed an upward shift in the binding energy of the Pd 3d core levels of 0.9 eV at the lowest Pd coverages, which slowly decayed toward the bulk value with increasing Pd coverage. These shifts were independent of the poling direction of the substrate and similar to those attributed to cluster size effects on inert supports. Thus, the spectroscopic data suggested that Pd does not interact strongly with LiNbO₃ surfaces. The surface chemical properties of the Pd clusters were investigated using CO temperature programmed desorption. On both positively and negatively poled substrates, CO desorption from freshly deposited Pd showed a splitting of the broad 460 K desorption peak characteristic of bulk Pd into distinct peaks at 270 and 490 K as the Pd coverage was decreased below 1.0 ML; behavior that also resembles that seen on inert supports. It was found that a small fraction of the adsorbed CO may dissociate (<2%) for Pd on both positively and negatively poled substrates. The thermal response of the smaller Pd clusters on the LiNbO₃ surfaces, however, was different from that of inert substrates. In a manner similar to Nb₂O₅, when CO desorption experiments were carried out a second time, the adsorption capacity decreased and the higher temperature desorption peak shifted from 490 K to below 450 K. This behavior was independent of the substrate poling direction. Thus, while there was evidence that LiNbO₃ does not behave as a completely inert support, no significant differences between positively and negatively poled surfaces were observed. This lack of sensitivity of the surface properties of the Pd to the poling direction of the substrate is attributed to the three-dimensional Pd clusters being too thick for their surfaces to be influenced by the polarization of the underlying substrate.     

Optical second-harmonic generation by supported metal clusters: Size and shape effects

Optical Second Harmonic Generation (SHG) by metal clusters has been investigated. For this purpose clusters were generated by the deposition and nucleation of metal atoms on a LiF(100) single crystal surface under ultrahigh vacuum conditions. The size and shape of the metal particles was characterized by optical transmission spectroscopy. The SHG intensity was detected in situ as a function of cluster size during the nucleation. Fundamental wavelengths of =1064 and 532 nm were used and the SHG signal was measured for different polarization combinations of the incident and registered light. SH radiation is detectable for particles as small as approximately 1 nm. The signal grows monotonically as a function of particle size, passes a maximum and finally drops off. This behavior is discussed in terms of resonant enhancement of the signal by surface plasmon excitation and changes of ⁽²⁾ as a function of particle size and shape. In further experiments the chemisorption of oxygen on the surface of the metal particles was studied. The SH signal decreases as a function of oxygen coverage and amounts to only about 15% of the initial value upon chemisorption of one monolayer. This indicates that the SH signal originates almost exclusively from the surface of the clean clusters and that higher order bulk contributions are negligible.     

EXAFS study of size dependence of atomic structure in palladium nanoparticles

Dependence of atomic structure of Palladium nanoparticles on supports Al₂O₃ and SiO₂ upon their size, changed from 1.3 to 10.5 nm, was studied by Pd K-edge EXAFS. To determine the structure of the interior (core) and the near surface regions of nanoparticle, the fitting technique of the Fourier-transforms F(R) of spectra was used, which enabled to overcome instabilities of the obtained structural parameters values. The processing of experimental data was performed using results of the study of features formation in │F(R)│ of Pd K-EXAFS in Pd foil. By this approach it was revealed that the local structure of Pd atoms in the core is similar to fcc structure of bulk Pd, irrespective of size. The percentage of Pd atoms, which can be attributed to the core, upon the particles size was determined and the obtained dependence was described by the “cluster size equation”. In the near surface region of nanoparticles, nearest-neighbors Pd–Pd distances show a large Debye–Waller parameters and the mean bond length slightly contracted for nanoparticles of sizes less than ~2 nm. The effect of small structural distortions in the vicinity of absorbing Pd atom in the near surface region was studied using the cluster model of nanoparticle.     

The catalytic activity of chemisorbed oxygen and carbon monoxide species on palladium and related metals investigated using SCF-Xα-SW calculations

Theoretical calculations of the electronic structure of small clusters modelling the adsorption of carbon monoxide on nickel and palladium and the adsorption of oxygen on palladium and platinum have been carried out using the SCF-Xα-SW method. Our results for the carbon monoxide-nickel clusters are in good agreement with earlier work. Comparing the carbon monoxide-nickel with the carbon monoxide-palladium results, suggests that the ordering of CO-derived cluster orbitals is the same in both cases but that the relative shifts are much different. In addition, the oxygen atom participates more significantly in the cluster containing palladium. An analysis of optical transition energies for Ni₅CO and Pd₅CO clusters is given and discussed in terms of experimental data regarding photodesorption of carbon monoxide. In the case of oxygen atoms in platinum and palldium clusters, we have used two different M₅O geometries: one in which the five metal atoms are in a single plane and oxygen is directly over a single metal atom (Type A) and a second in which the oxygen atom is coordinated to four sur face metal atoms and is directly over a metal atom in the second layer (Type B). The levels calculated for the Pd50 type B cluster are in good agreement with available UPS data. Significant differences in type A and type B clusters are noted for palladium. The results can be correlated with experimental Auger spectroscopic and kinetic data. In particular, the type A oxygen cor relates well with an experimentally observed very reactive species, while type B oxygen cor relates well with a quite unreactive species. These two types also correlate with two species observed by Auger spectroscopy.     

Oxidation of GaN{0001}-11 surfaces at room temperature

The interaction of unexcited oxygen molecules with clean GaN{0001}-11 surfaces was investigated using X-ray photoemission spectroscopy (XPS), Auger electron spectroscopy (AES), and low-energy electron diffraction (LEED). Clean surfaces were prepared by a HF dip followed either by desorption of Ga films deposited at room temperature or by nitrogen-ion bombardment and annealing. During exposures in the range from 0.3 up to 10¹⁵ L-O₂ any excitations of the oxygen were avoided. Oxygen coverages determined from the XPS and the AES data differ by a factor of two. The larger XPS-derived coverages are considered to be more reliable since the AES signals decayed during data recording. The oxygen uptake takes place in two consecutive stages. The first one is identified as dissociative chemisorption and the second one is tentatively attributed to field-assisted diffusion by the Mott-Cabrera mechanism. The dissociative chemisorption is characterized by an initial sticking coefficient of and a saturation coverage of monolayers that is reached after exposures of 10³ L-O₂. The second mechanism sets in at exposures to 10⁸ L-O₂ but reaches no saturation even with the largest doses applied. Received 4 September 1998 and Received in final form 6 November 1998     

Control and enhancement of structural and magnetic properties of Co/Pd multilayer by seeded epitaxy

Effects of Co seed layer on the structural and magnetic properties of Co/Pd multilayers have been studied. Reflection high-energy electron diffraction measurements showed a possible control of the crystal orientation of Pd buffer layer from polycrystalline to face-centered cubic (111) orientation when using Co seed layer. Additionally, atomic force microscopy observations confirmed the ability of Co seed layer to flatten the Pd buffer layer drastically. In fact, the usage of Co seed layer has decreased the root-mean-square roughness from 2.3 to 0.23 nm. As for controlling the structural properties of Pd buffer layer, the effective perpendicular magnetic anisotropy constant was enhanced, mainly by the improvement of surface anisotropy. Electronic states of α-Al₂O₃(0001)/metal interface obtained by electron energy loss spectroscopy proved that these differences were the fruit of the interaction between the metal layer and oxygen atoms on the Al₂O₃(0001) surface.     

Effects of O defects on adsorption of small Ag clusterson a MgO(001) surface

The interaction of Ag atoms with a defective MgO(001) surface is systematically studied based on density functional theory. The Ag clusters are deposited on neutral and charged oxygen vacancies of the MgO(001) surface. The structures of Ag clusters take the shape of simple models of two- or three-dimensional (2D and 3D) metal particles deposited on the MgO surface. When the nucleation of the metal clusters occurs in the F_s (missing neutral O) centre, the interaction with the substrate is considerably stronger than that in the F_s⁺ (missing O^- ) centre. The results show that the adsorption of Ag atoms on the MgO surface with oxygen vacancy is stronger than on a clear MgO surface, thereby attracting more Ag atoms to cluster together, and forming atomic islands.