Chemically shifted surface core-levels and surface segregation in EuAu and YbAu alloys

Chemically shifted surface core-level binding energies are observed for the rare-earth alloy component in Eu_1?xAu_x and Yb_1?xAu_x. Furthermore, these shifts are different from the chemical shifts of the bulk 4f levels. The surface core-levels are used to identify surface segregation of the lanthanide metal in the present alloys.     

Core hole satellites in Ni and Au Ni

The 2p core hole satellite structure in Ni and 5% Ni in Au are compared and discussed in terms of recent theoretical models. The large differences found for these two materials are explained in terms of the large differences in the Ni 3d band, and virtual bound state widths. The satellite structure for Au Ni is found to agree with the multiplet splitting of the free atom in a 2p⁵3d⁹ configuration.     

Core level photoemission study of the adsorption of iodine on Ni{100}

Synchrotron radiation photoemission from the Ni 3p and I 4d core levels has been studied for iodine adsorbed on Ni{100} in a range of different phases. In the range of chemisorbed structures involving overlayer compression from coverages θ of about 0.3 to 0.4 the I 4d photoemission binding energies decrease by ~0.3 eV, while further compression to a c(2 × 2) structure leads to a further decrease by ~0.4 eV. Low temperature adsorption of molecular iodine shows a binding energy of 0.1 eV lower still. In the chemisorbed coverage range these core level shifts are found to be substantially less than the I-I repulsive energy interactions and are associated with the through-metal component of this interaction, while the residual component concealed from the photoemission experiments is attributed to through-space overlap interaction. Other processes which may contribute to the observed binding energy shifts, including Coulomb interactions in both initial and final states, are discussed in some detail.     

Core level photoemission study of Au deposited on Pt(111) in the submonolayer range

A photoemission study, using a synchrotron source, on the deposition of submonolayer amounts of Au on Pt(111) has been performed. The Au 4f emission shifts continuously to higher binding energies for increasing Au coverages. A good fit to the experimental spectra has been obtained by only one Doniac-Sunjic function. We discuss the initial versus final state effects in photoemission experiments on small supported particles.     

XPS study of bonding in ligated Au clusters

Ligated metal cluster compounds containing a core of metal atoms with well defined structure surrounded by a variety of organic and inorganic ligands are closely related to the bare metal clusters that are only now becoming available in uniform cluster size. The evolution of band structure and the development of metallic properties as a function of cluster size are of considerable interest. We report here a comparison of these two types of systems based on a study by X-ray photoelectron spectroscopy. The valence band spectra of ligated Au clusters compounds are similar in many respects to those of bare clusters, indicating significant participation of the d electrons in bonding. The core electron binding energy shifts of the central Au atom in Au₁₁(PPh₃)₇Cl₃ corresponds to the loss of approximation one 6 s electron. The total charge transferred to the halogens is accounted for by the shifts of the central and three halogenbonded Au atoms. No indication of metallic behaviour is found in the core of the ligated clusters.     

Computer simulation of solute segregation to a Σ = 5 tilt boundary in Au,Cu and Ni

A Lattice Energy Function that combines a Mie type interatomic potential and a free electron gas volume dependence has been applied to the study of grain boundary energy and structure of a Σ = 5 tilt boundary in Au, Cu and Ni and of solute segregation to the same. Interatomic potentials and volume dependencies of the solvent and solute were adjusted to fit the relative partial molar enthalpy and volume at infinite dilution order to construct a AB type potential and volume dependence. This AB interaction is then applied to calculate the binding energies of solute to various grain boundary sites and the resulting change in grain boundary energy. A relationship between the binding energy and change in grain boundary is derived. The relative values of the grain boundary energy are in agreement with experimental values of the average grain boundary energies. The relative binding energies of the tested solvent-solute systems are in agreemnet with expectations that certain systems should have larger binding energies than others. The behavior of solute binding energies and local relaxations are in agreement with other studies of grain boundary segregation which use different Lattice Energy Functions and relaxation algorithms. The change in grain boundary energy is shown to be directly proportional to the binding energy.     

Core-level binding energy shifts in dilute alloys

Core level binding energy shifts for the element A of a large number of dilute alloys AB have been measured, where the concentration of the dilute component A is 10% or less. The experimental shifts are analysed in terms of alloy heat of formation data, for which we have used Miedema's semi-empirical scheme. Good overall agreement is obtained between the experimental data and the calculated values, encouraging the use of electron spectroscopy for evaluating solution energies of metallic systems.     

Core hole satellites in NixPd1-x alloys

The two and three hole satellites accompanying the main Ni 2p and Pd 3d XPS core lines in Ni_xPd_1-x alloys have been measured as function of the alloy concentration. The changes in satellite distance with concentration cannot be explained by the thermochemical approach, which has recently been shown to describe successfully the one hole core level binding energy shifts (main line) in alloys. The reason is probably, that in this approach, which uses thermochemical data of Z + 1, Z + 2 and Z + 3 elements - where Z stands for Ni or Pd and Z + n is the nth element following them in the periodic table - d-band contributions to the cohesive energies of the final d-hole states are neglected.     

The effect of gold on platinum oxidation in homogeneous Au-Pt electrocatalysts

Oxidation of Au-Pt thin films was carried out in ambient air at room temperature and characterized by X-ray photoelectron spectroscopy. The homogeneous films were prepared by RF co-sputtering with concentrations varying from Au₉Pt₉₁ to Au₈₉Pt₁₁ and compared to pure Pt and Au thin films. Spectral deconvolution of the Au 4f and Pt 4f core levels revealed linear peak shifts for both the Au-Au and Pt-Pt bonding components as a function of alloy mixture and metallic component peak asymmetry that remained constant for all alloy stoichiometries. The predominant oxidation products were PtO and PtO₂ and were characterized by stable core level binding energies for all films. A gradual decline in the Pt-O_x products and corresponding levels of elemental oxygen was observed with increasing Au content but was similar in proportion to the metallic Pt components. Based on these results, variations in Pt oxide phases and/or concentration do not appear to contribute to enhanced electrocatalytic activity for oxygen reduction observed for the intermediate alloy stoichiometries.     

Charged pions from Ni on Ni collisions between 1 and 2 AGeV

Charged pions from Ni + Ni reactions at 1.05, 1.45 and 1.93 AGeV are measured with the FOPI detector. The mean π^± multiplicities per mean number of participants increase with beam energy, in accordance with earlier studies of the Ar + KCl and La + La systems. The pion kinetic energy spectra have concave shape and are fitted by the superposition of two Boltzmann distributions with different temperatures. These apparent temperatures depend only weakly on bombarding energy. The pion angular distributions show a forward/backward enhancement at all energies, but not the Θ = 90⁰ enhancement which was observed in case of the Au + Au system. These features also determine the rapidity distributions which are therefore in disagreement with the hypothesis of one thermal source. The importance of the Coulomb interaction and of the pion rescattering by spectator matter in producing these phenomena is discussed.     

Electron-phonon interaction and coulomb pseudopotential in AuGa alloys from resistivity and superconductivity measurements

Measurements of the electrical resistivity as a function of temperature from 250 to 270 K for Au and f.c.c. phase AuGa alloys are presented. The linear dependence of the resistivity with temperature and previous results of the superconducting transition temperature of the alloys are used to obtain a value for T_c of pure Au. From these results a new method is introduced to estimate the Coulomb pseudopotential μ¹ for gold.     

Forward and backward electron emission cross-sections for 23 MeVu<Superscript>-1</Superscript> C,Ni and Au projectiles traversing C,Al , Ni,Ag , Au and Bi foils

A rather complete experimental study of forward and backward electron velocity spectra from thin foils bombarded with ions at constant velocity of 30 atomic units (23MeV u^-1) was performed. Three different beams ( ¹²C³⁺ , ⁵⁸Ni¹⁴⁺ and ¹⁹⁷Au³⁶⁺ and six different targets ( ¹²C , ²⁷Al , ^natNi , ^natAg , ¹⁹⁷Au and ²⁰⁹Bi of approximately 90μg cm^-2 thickness were used. This procedure allowed to study the evolution of electron emission (velocity and angular distributions) for the [projectile; target] matrix [ C , Ni , Au ; C , Al , Ni , Ag , Au , Bi ] in a wide angular range. The projectile and target dependence of absolute cross-sections for binary encounter-, Auger- and backward-emitted electrons are analyzed.     

X-ray photoelectron spectroscopy of Ni in Ni–Zn and Ni–Al alloys

X-ray photoelectron spectroscopy measurements on Ni in the alloys Ni, Ni₅₀Zn₅₀, Ni₂₀Zn₈₀ and Ni₅₀Al₅₀ have been made and confirm previous measurements of the band structure. The satellite lines on the Ni 2p and 3s lines are found to be present in the spectra even when the density of 3d states at the Fermi energy is low.     

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).     

Site Preference and Alloying Effect of Excess Ni in Ni-Mn-Ga Shape Memory Alloys

The formation energies and electronic structures of Ni-rich Ni-Mn-Ga alloys have been investigated by firstprinciples calculations using the pseudopotential plane wave method based on density functional theory. The results show that the alloying Ni prefers to occupy the Mn site directly in Ni9Mn3Ga4 and to occupy the Mn site and drive the displaced Mn atom to the Ga site in NigMn4Ga3, which is in accordance with the experimental result. According to the lattice constants and the density of states analyses, these site preference behaviours are closely related to the smaller lattice distortion and the lower-energy electronic structure when the excess Ni occupies the Mn site. The effect of Ni alloying on martensitic transformation is discussed and the enhancement of martensitic transformation temperature by Ni alloying is estimated by the calculated formation energy difference between austenite and martensite phases.     

Surface core-level binding energy shifts in alloys

A simple theory for the core-level binding energy shifts at the surfaces of binary alloys A_xB_1?x is presented. Results are given for the surface core-level shifts of Ni in Ni_xCu_1?x alloys and Pd in Pd_xAg_1?x alloys. It has been shown that the surface core-level shifts may depend sensitively on surface segregation.     

Molecular cluster calculations for the interpretation of CO chemisorption on a Ni(100) surface

Self-consistent Hartree-Fock-Slater molecular cluster calculations for the chemisorption of carbon monoxide on a Ni(100) surface are presented. In earlier calculations of this type the CO molecule has been assumed to be chemisorbed in a hollow position of C_4v symmetry. A recent EELS experiment shows however that in the most stable configuration CO is linearly bonded to the Ni atoms, i.e. a top position of the CO-molecule. This experiment indicates also that there exists an additional bridge bonding of the CO molecule to the two nearest neighbour Ni atoms. The variation of the energy levels, binding energies and charge distribution with the height of the CO molecule above the nickel surface is calculated for the top position using the NiCO and Ni₅CO clusters and for the bridge bonding configuration using the Ni₂CO cluster. The CO 1π level is found to be split by about 0.8 eV in bridge bonding geometry. For both hollow and top positions the 1π and 5σ levels are separated by about 0.5 eV. The energy separation to the 4σ level is about 3 eV, which is in good agreement with experimental data. Theoretical ionization energies relative to the Fermi energy for top position geometry at a bond distance of 3.5 au between the carbon atom and nickel surface were found to be 25.7, 11.7, 8.7 and 8.2 eV for the 3σ, 4σ, 5σ and 1π levels which should be compared with the experimental data of 29.0, 10.8, 8.4 and 7.8 eV, respectively. The corresponding ionization energies for a bond angle of 99° in bridge bonding were 23.7, 12.1, 7.3, 7.0 and 7.9 eV. The two last values represent the 1π level which is split into two levels in this geometry. The variation of the C-O stretch vibrational frequencies with the height of the CO molecule above the surface for the top-position geometry is estimated from the 5σ and 2π gross orbital populations and from the CO σ and π overlap populations.     

Experimental valence-band study of Ti(NiCu) alloys with different compositions and crystal structures

The density of valence-band electronic states of Ti(NiCu) alloys with different crystal structures and elemental compositions has been studied by X-ray photoelectron spectroscopy. It has been established that the change in the crystal state initiated by a martensitic transformation or a transition from the amorphous state to the crystal state does not affect the valence-band electronic state density distribution of the Ti₅₀Ni₅₀ and Ti₅₀Ni₂₅Cu₂₅ alloys. It has been shown that a change in the elemental composition leads to a noticeable redistribution of the electronic density in alloys of the Ti₅₀Ni_{50 ? x} Cu _x system (x = 0, 10, 15, 25, 30, 38, 50 at. %). As the copper concentration in the Ti(NiCu) alloys increases, the contribution of the Ni d states in the vicinity of the Fermi level decreases, with the d band of nickel shifting toward higher binding energies, and that of copper, toward lower binding energies.     

Onset of nuclear matter expansion in Au+Au collisions

Using the FOPI detector at GSI Darmstadt, excitation functions of collective flow components were measured for the Au+Au system, in the reaction plane and out of this plane, at seven incident energies ranging from 100A MeV to 800A MeV. The threshold energies, corresponding to the onset of sideward-flow (balance energy) and squeeze-out effect (transition energy), are extracted from extrapolations of these excitation functions toward lower beam energies for charged products with Z ⩾ 2. The transition energy is found to be larger than the balance energy. The impact parameter dependence of both balance and transition energies, when extrapolated to central collisions, suggests comparable although slightly higher values than the threshold energy for the radial flow. The relevant parameter seems to be the energy deposited into the system in order to overcome the attractive nuclear forces.     

Alloy formation of Co/Ni/Pt(1 1 1)

The initial growth and alloy formation of ultrathin Co films deposited on 1 ML Ni/Pt(1 1 1) were investigated by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and ultraviolet photoelectron spectroscopy (UPS). A sequence of samples of d_Co Co/1 ML Ni/Pt(1 1 1) (d_Co = 1, 2, and 3 ML) were prepared at room temperature, and then heated up to investigate the diffusion process. The Co and Ni atoms intermix at lower annealing temperature, and Co-Ni intermixing layer diffuses into the Pt substrate to form Ni-Co-Pt alloys at higher annealing temperature. The diffusion temperatures are Co coverage dependent. The evolution of UPS with annealing temperatures also shows the formation of surface alloys. Some interesting LEED patterns of 1 ML Co/1 ML Ni/Pt(1 1 1) show the formation of ordered alloys at different annealing temperature ranges. Further studies in the Curie temperature and concentration analysis, show that the ordered alloys corresponding to different LEED patterns are Ni_xCo_1−xPt and Ni_xCo_1−xPt₃. The relationship between the interface structure and magnetic properties was investigated.