First-principles studies: Thiolated Au2Cr and Au6Cr clusters

The structural, energetic and magnetic properties of thiol-passivating Au₂Cr and Au₆Cr clusters are investigated by performing first-principles calculation based on density functional theory. We find that the adsorption of thiolate is energetically more favorable than thiol and that the thiolates favor “top” site adsorption on Cr atom in one methanethiolate adsorbed Au₂Cr cluster while they favor “bridge” site adsorption on top of the middle point of Cr–Au bonds in three methanethiolates adsorbed Au₂Cr cluster. In thiol-passivating Au₆Cr cluster, the thiol favor “top” site adsorption on top of atom Au while the thiolate favor “bridge” site adsorption on top of the middle point of Au–Au bonds. The energetics of the reactions indicates that these thiol-passivating Au₂Cr or Au₆Cr clusters can be used as hydrogen storage materials. There are large and positive spin populations on atom Cr. The spin populations of atoms Au, S and H are attributed to both the spin delocalization and the spin polarization mechanisms.     

On the direct contact between overgrowth and substrate through amorphous carbon layers

The influence of intermediate amorphous carbon layers of different thicknesses on the epitaxy of Cu on Au (111) platelets was investigated. The experimental results prove that under experimental conditions for which the so called “long range” effect has been detected, direct contact between overgrowth and substrate through the intermediate layers is possible, provided its thickness is below a certain critical value. For carbon films prepared at room temperature on Au (111) substrates in a vacuum of 10^?6 Torr, this value lies between 50A?and 70A?.     

The epitaxy of gold on (110) tungsten studied by leed

Growth of gold condensed on the (110) plane of tungsten has been studied using LEED and AES. Three ordered surface structures were observed when condensation takes place at or above 700 K, and no detectable order is seen below this temperature. Structure 1 is developed as the coverage approaches one monolayer and has gold atoms held in the W(110) array with a resultant 2% reduction in gold atom diameter. The second gold layer adopts the Au(111) structure with $\text{Au}\text{[1}\text{2}\text{1]}$ rotated by 2.5° from $\text{W}\text{[1}\text{1}\text{0]}$ and the first gold layer may also be constrained to adopt this structure. Deposition of more gold produces three dimensional crystallites with Au(111)∥W(110) which are double-positioned with their 121 directions parallel to the 121 directions of tungsten. Addition of half a monolayer of oxygen before condensation, completely prevents formation of structures 1 and 2. Instead, at coverages of 3 or more monolayers, three dimensional crystallites develop with Au(111) ∥ W(110) and $\text{Au}\text{[1}\text{2}\text{1] ∥}\text{W}\text{[1}\text{1}\text{0]}$. This behaviour is compared with the reported behaviour of copper and silver on W(110).     

Leed and Aes study of the Au/AuPb2 interface

The adsorption of lead on gold at room temperature in UHV conditions has been studied by LEED and AES. We review some of the data obtained on the Au(100), (111), and (110) faces, published elsewhere, and we give some new experimental results on the stepped Au(S) [n(100) × (111)] (with n = 3, 4, 5, and 6) faces. On all these faces, as lead is deposited on the gold substrate it first forms a monolayer of lead, then a compound AuPb₂. Using the LEED and Auger data we give a model of the epitaxy with a layer-by-layer growth mechanism. We propose a model which involves a transition alloy wich forms at the interface Au/AuPb₂. This model is in agreement with the LEED diagrams observed before the one corresponding to bulk AuPb₂. In the case of the epitaxy of lead on gold (100), we calculate the Auger peak-to-peak ] heights of the gold (72 eV) and lead (93 eV) transitions versus coverage. We obtain good agreement with the experimental data, assuming that the first and last layers of the alloy are lead monolayers and diffusion of lead in gold as well as gold in lead.     

Dispersion of low frequency phonons in the deuterated naphthalene crystal

The dispersion curves of the external and the four lowest internal phonon modes in d₈-naphthalene (C₁₀D₈) crystal have been measured by coherent inelastic neutron scattering for the [010] and [100] directions at 98K and partially at 5K. The results are compared with calculations based on model atom-atom “6-exp” potential with the Kitaigorodski set of parameters for C-C, C-H and H-H interactions.     

Structural phase transition and structural properties in oxygenated La2CuO4+y; y ∼0.02

The crystal structure of the oxygenated La₂CuO_4+y; y ～0.02 has been studied by X-ray diffraction. It is found that the structural phase transition from tetragonal to orthorhombic symmetry occurring at about 450 K (Tc) is of second order and shows diffuse scattering above Tc. The diffuse scattering is related to static and/or dynamic short-range order of cooperative tilts of rigid-like elongated CuO₆ octahedra, which make two-dimensional networks stacked along the [001] axis. The structures at room temperature and 210K are determined using a 4-circle X-ray diffractometer and have the orthorhombic space group ¹⁰D_2h-Pccn. The structure is mainly characterized by anisotropic cooperative tilts of the CuO₄ octahedra around the [100]_p and [010]_p primitive axes in two-dimensional octahedron-networks, where suffix “p” means pseudo K₂NiF₄-type structure. The anisotropy of the tilting-angles results from pushing by excess oxygen atoms to apical oxygen atoms of the CuO₆ octahedra. It is also found by refinement of the structure that the excess oxygen atoms are randomly sited at the atomic coordinates (1/4,1/4,0.244) and/or (1/4, 1/4,0.279).     

Charging effects on the vibrational properties of Au and Au2 on MgO(100)

Vibrational spectra of charge-neutral and charged Au and Au₂ on MgO(100) were investigated using ab-initio density functional perturbation theory. The calculated vibrational spectra showed vibrational features associated with the charge states of Au and Au₂ on MgO(100). Further analyses of surface in-plane and normal phonon modes of Au and Au₂ on MgO(100) were performed to extract vibrational features involving the Au modes. These features provide important information for experimentally explaining the charge states of Au and Au₂ on MgO(100).     

Generalized susceptibilities and phonon anomalies in Pd and Pt metals

The generalized susceptibility, χ(q), in Pd and Pt for q along the [100], [110], [111], and [120] directions was determined from their APW and RAPW energy band structures, respectively, using the analytic tetrahedron linear energy scheme of Rath and Freeman. The band structures were previously found to yield Fermi surface radii, temperature dependencies of the static magnetic susceptibility, χ(T), resistivity, and a spin lattice relaxation, T₁T, in very good agreement with experiment. In the χ(q) calculations, we used 2048 tetrahedra in 1/48th irreducible BZ and the energy eigenvalues for bands 4, 5, and 6 which cross the Fermi energy as fitted to a Fourier series representation. The intraband parts of χ(q) at q = 0 for both metals are found to agree with the density of states at the Fermi energy to without 0.5%. Our results show that the dominant contribution to χ_intra arises from the dominant band 5 whose “jungle-gym” FS has strong nesting features; the main peak for Pd occurs at the same q value (= 0.65π/a) for q along the [0q0], [q, q, 0], and [q, q, q] directions. The locus of this main peak is a square in the (0, 0, 1) plane. The maximum of χ_intra for q along the [110] and [111] directions are 23% and 13%, respectively, higher than the value of χ(q) at q = 0. For q along the [010] and [120] directions, the peak is, however, lower than the value of χ_intra at q = 0. Hence, while phonon anomalies are predicted for the [110] and [111] directions, no anomaly is predicted for either the [100] or [120] direction. The predicted q value for the [110] anomaly, $\text{q}\text{= 0.65π/a}$ is close to the experimental value of ～0.7 π/a. Although there may be a hint of an anomaly at 0.56 [111] in the measurements, a more detailed investigation of this region is called for. For platinum, χ_intra for q along the [010], [110] and [111] directions has main peaks which occur at q = 0.68 π/a, 0.75 π/a, and 0.85 π/a, respectively. Here too, this main peak comes from the nesting of the jungle-gym Fermi surface which is not, however, as flat as that of palladium. Anomalies are predicted (although weaker in Pt than in Pd) along [110] and [111] but not along [100] and [120]. The [110] anomaly is close to the measured q value (～0.7–0.8 π/a). Also in agreement with experiment, we predict a weaker [110] anomaly for Pt than for Pd. In both Pd and Pt, weaker anomalies are predicted for the [111] direction than for the [110] direction.     

Light-emitting Si: Er structures prepared by molecular-beam epitaxy: Structural defects

The structural defects in silicon layers grown by molecular-beam epitaxy and doped with erbium up to concentrations [Er] = 4 × 10¹⁹ cm^?3 are studied using transmission electron microscopy and high-resolution electron microscopy. It is established that the main types of extended structural defects at erbium concentrations [Er] ≥ 2 × 10¹⁹ cm^?3 are 4-to 25-nm Er spherical precipitates located at the “epitaxial layer-substrate” boundary and platelike ErSi₂ precipitates residing in the { 111} planes throughout the thickness of the layer.     

A molecular dynamics study of the structural change differences between Au225 and Au369 clusters on MgO surfaces at low temperature

The differences in structural change between Au₂₂₅ and Au₃₆₉ clusters with their (111) facets supported on MgO(100) surfaces at 5 K are studied by using molecular-dynamics simulations with the atomic interchange potentials of the Au/MgO interface. The parameters are obtained from the ab initio energies using the Chen-Möbius inversion method. Analyses of the pair distribution functions show that the two Au clusters use different deformation processes to adjust the distances between the interface atoms, owing to the misfit between the atom distances among the clusters and the substrates. The local structural changes are identified by atomic density profiles.     

Surface interactions of Au(I) cyclo-trimer with Au(111) and Al(111) surfaces: A computational study

A plane-wave density functional theory (DFT) study on surface interactions of a cyclo-[Au(μ-Pz)]₃ monolayer (denoted as T), Pz = pyrazolate, with Au(111) and Al(111) surfaces (denoted as M′) has been performed. Structural and electronic properties at the M′–T interfaces are determined from individually optimized structures of M′, T and M′–T. Results show that the gold pyrazolate trimer (T) binds more strongly on the Au(111) surface than on Al(111). Charge redistribution has been observed at both M′–T interfaces, where charge is “pushed” back towards the Au(111) surface from the trimer monolayer in Au(111)–T system, while the opposite happens in the Al(111)–T system where the charge is being pushed toward the trimer monolayer from the Al(111) surface. Considerable changes to the work function of Au(111) and Al(111) surfaces upon the trimer adsorption which arise from monolayer vacuum level shifts and dipole formation at the interfaces are calculated. The interaction between cyclo-[Au(μ-Pz)]₃ with metal surfaces causes band broadening of the gold pyrazolate trimer in M′–T systems. The present study aids better understanding of the role of intermolecular interactions, bond dipoles, energy-level alignment and electronic coupling at the interface of metal electrodes and organometallic semiconductor to help design metal–organic field effect transistors (MOFETs) and other organometallic electronic devices.     

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.     

Magnetoresistance of epitaxial SrRuO3 thin films on a flexible CoFe2O4-buffered mica substrate

We have investigated the magnetoresistance of epitaxial SrRuO₃ (SRO) thin films on a flexible CoFe₂O₄ (CFO)-buffered mica substrate. High-resolution X-ray diffraction and transmission electron microscopy revealed that the SRO film could be epitaxially grown on a mica substrate with a 22-nm-thick CFO buffer layer. The epitaxial relationships were SRO [1–10] || CFO [1–10] || mica [010] and SRO [111] || CFO [111] || mica [001]. Epitaxial SRO thin films exhibited two magnetoresistance (MR) peaks; one peak occurred at a Curie temperature of 160 K (HT-MR) and the other at a low temperature of 40 K (LT-MR). The LT-MR increased more rapidly with an increase of the buffer layer thickness than the HT-MR. The LT-MR was similar for the two orthogonal current directions with respect to the magnetic field. We explained the HT-MR and LT-MR in terms of the suppression of spin fluctuations and the magnetic rotation of crystallographic domains, respectively.     

Monazite (monoclinic LaPO4) slip systems at room temperature

Polycrystalline monazite (monoclinic LaPO₄) was deformed by spherical indentation at room temperature. Slip systems were identified using TEM of thin sections prepared parallel and close to the indented surface. Dislocation Burgers vectors (b) were identified by Burgers circuit closure in high resolution TEM images, supplemented by diffraction contrast where possible. A total of 441 b determinations were made in 97 grains. The most common slip systems were [001]/(010), [100]/(010) and [010]/(100). Slip on (001) was less common. Many other less common slip systems and Burgers vectors were also identified, including b = [101], [101], [011], [110] and [111]. b = [101] dislocations dissociate into ½[101] partials, and b = [101] dislocations are inferred to dissociate to ½[101] partials, with a low energy stacking fault of ～30 mJ/m². b = [100] dislocations may dissociate into ¼[210] + ¼[210] partials. b = [010] may sometimes dissociate to ½[010] + ½[010] partials. Other types of partial dislocations were also observed and discussed. All partial dislocations were climb dissociated. The line energies of monazite dislocations and their partials were calculated, and stacking fault structures for partial dislocations are analyzed. Satisfaction of the Von Mises criterion for full ductility most likely involves [101]/(111) and ?011?/{011} or {111} slip, but other combinations that require both b = [101] and ?011? or ?110? are possible. If deformation twinning is active, slip systems with b = ?011? or ?110? may not be necessary for full ductility.     

Dual-oriented thin crystals of molybdenum grown under Ar+ ion bombardment

Ar⁺ sputtering of an Cu(111) surface while simultaneously supplying Mo atoms is known to induce an oriented growth of Mo thin crystals, or seed-layers, on evolving conical Cu protrusions. The seed-layers thus formed are shown to be dual-oriented, or bicrystalline, consisting of columnar crystallites grown homo-epitaxially. The orientation relationship between the two types of crystallites was (100)_I (111)_II with [001]_I [110]_II, and this bicrystallinity probably resulted from a non-uniform charge-up of the layers' growth front. As concluded from high-resolution electron microscopy, the Mo(100) stacking is elastically converted into the Mo(111) stacking and vice versa, under the influence of tensile stress. The homo-epitaxy that the seed-layers exhibited is believed to reflect the mutual convertibility of the Mo(100) and (111) stackings.     

Structural evolution of glutathionate-protected gold clusters studied by means of 197 Au Mössbauer spectroscopy

¹⁹⁷Au Mössbauer spectra of a series of glutathionate-protected gold clusters, Au _n (SG) _m , with n = 10 ? ~55, were re-analyzed to understand the structure evolution behavior. The numbers of gold atoms coordinated by different numbers (0, 1, and 2) of the GS ligands were successfully determined by assuming individual isomer shifts and quadrupole splittings for the three sites in Au₂₅(SG)₁₈ (Tsukuda et al., Chem Lett 40:1292, 2011). The analysis revealed the drastic structural evolution of Au _n (SG) _m in the range of n = 10 ? ~55. In Au₁₀(SG)₁₀, all the gold atoms are bonded to GS ligands, indicating –Au–S(G)– cyclic structures. A catenane structure was proposed for Au₁₀(SG)₁₀. At n = 25, a single Au atom without the GS ligation appeared, consistent with the formation of an icosahedral Au₁₃ core protected by six staples, –S(G)–[Au–S(G)–]₂. At n = 39, it is considered that Au₃₉(SG)₂₄ has a similar structure to that of Au₃₈(SC₂H₄Ph)₂₄ with face-fused bi-icosahedral Au₂₃ core.     

Evolution of structures,stabilities, and electronic properties of anionic [AunRb]− (n = 1–10) clusters: comparison with pure gold clusters

The geometric structures, stabilities, and electronic properties of small size anionic [Au_nRb]^? and Au_n+1^? (n = 1–10) clusters have been systematically investigated by using density functional theory. The optimised geometries show that the structures of [Au_nRb]^? clusters favour the three-dimensional structure at n ≥ 8. The Rb atoms tend to occupy the most highly coordinated position and form the largest probable number of bonds with gold atoms. One Au atom capped on [Au_n-1Rb]^? structures is the dominant growth pattern for n = 2–8 and Rb atom capped on Au_n^? structures for n = 9–10. The averaged atomic bonding energies, fragmentation energies, second-order difference of energies, and highest occupied molecular orbital–lowest unoccupied molecular orbital gaps exhibit a pronounced even–odd alternations phenomenon. The charges in [Au_nRb]^? clusters transfer from the Rb atoms to Au_n host. In addition, it is found that the most favourable dissociation channel of the [Au_nRb]^? clusters is to eject a Rb atom and the highest energy dissociation path is Rb^? anion ejection.     

Internal field distribution around spin-glas freezing temperature in AuFe-alloys

We demonstrate an application of PAC to the study of magnetic ordering in random alloys. Using¹¹¹Cd as a probe the spin-glass freezing inAuFe-alloys of different concentrations could be observed. In the Au₈₂Fe₁₈ alloy no indication of ferromagnetism above the freezing temperature was found, due to the fact that the¹¹¹In probe nuclei are located in a Au rich environment.     

Au/In bilayers studied with 111In deposited at the interface

Au/In bilayer samples of different stoichiometries were studied using the time-differential perturbed angular correlation technique. The ¹¹¹In probe atoms were deposited at the gold/indium interface to follow the formation of the intermetallic compounds at an early stage. Au-In phases of different composition (AuIn₂, AuIn, Au₇In₃, Au₃In) were created at the interfaces upon annealing. In addition a metastable Au₇In₃(m) phase, observed only after quenching in the bulk Au_0.7In_0.3 alloy, was found. This revised version was published online in August 2006 with corrections to the Cover Date.     

Crystal habits of Pd and Pt particles: Nature of surface sites

Morphology of small Pd and Pt crystallites prepared by vacuum condensation has been studied by electron microscopy so as to determine the surface sturcture. A high resolution dark field technique is used to obtain the crystallite shape. It was found that in a range of size 60–200 Å most crystallites are bordered by incomplete (111) layers which give a large number of surface “B₅ sites”.