Confined Shockley surface states on the (111) facets of gold clusters

Combining low-temperature scanning tunneling microscopy and spectroscopy with high-resolution ultraviolet photoemission, we have revealed a confined Shockley surface state on the (111) facets of gold clusters with about N=10(4) atoms grown in nanopits on highly oriented graphite. With tunneling spectroscopy, we observed energy dependent nodal patterns in the dI/dV maps, which are in quantitative agreement with the two-dimensional confinement of the surface state within the hexagonal facet area. The results indicate that the lattice of the ionic cores influences the electronic properties of the clusters significantly.     

An interpretation of the conditions for the existence of Shockley surface states

A study is made of the Shockley surface states in a linear chain of equal atoms, joined by alternately strong bonds. If the simple MO LCAO method is used, which considers the exchange integrals between nearest neighbours and next nearest neighbours, we get the surface states for a semi-infinite chain if the stronger bond is interrupted. The connection between Shockley and Tamm surface states is shown and the hypothesis is put forward that the condition for the existence of Shockley surface states has a generally simple physical interpretation, the validity of which is proved on the models of a semi-infinite crystal studied up to now.

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Shockley surface states for a graphite and diamond model with a delta function potential

The Shockley surface states problem was formulated for the Coulson graphite model and Hoerni diamond model with delta function potentials. It was shown that the solution of these problems can be reduced to the solution of analogous problems in the MO-LCAO method. A solution is given for one type of models. The analogy of both methods shows that the qualitative properties of Shockley surface states depend primarily on the geometry of the lattices.

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Equilibrium surface segregation of dissolved nonmetal atoms on iron(100) faces

At elevated temperatures equilibria of surface segregation X (dissolved) = X (adsorbed) have been studied for the nonmetal atoms X = C, N and S. Iron single crystals with (100)orientation have been doped with different concentrations of solute atoms (in the range about 10–100 wt ppm). The samples were introduced into the UHV chamber, cleaned and then heated to temperatures in the α-solid solution range. The surface concentration of the segregated nonmetal atoms was observed by AES for different bulk concentrations in dependence of the temperature. The LEED pattern was also observed during segregation equilibrium at temperatures up to about 750° C. The LEED patterns indicate a c(2 × 2) structure for carbon and nitrogen as well as for sulfur. The temperature dependence of the surface concentration for carbon on Fe(100) can be described by a Langmuir-McLean equation, an average segregation enthalpy of ?85 kJ/mol°C is obtained. Since N₂ desorption occurs the nitrogen segregation is in virtual equilibrium only at temperatures <500°C. The equilibrium surface concentration of sulfur on α-iron is virtually independent of the solute concentration and the temperature: there is always a saturated layer of sulfur on the (100) faces, even at small bulk concentrations. Since the thermodynamic activity of the nonmetal atoms is well defined in the segregation studies (except nitrogen at higher temperatures) , the results can be correlated with studies in gas atmospheres at atmospheric pressure. The relations to the kinetics of the carburization and the nitrogenation of iron are discussed and the influence of sulfur on these reactions.     

Electronic quasiparticle structure of ferromagnetic bcc iron

We investigate the influence of electron correlations on the temperature-dependence of the electronic structure of ferromagnetic bcc iron by use of a manybody evaluation of a generalized model of magnetism. The single-particle part of the model-Hamiltonian is taken from an LDA band structure calculation. The manybody interactions are described by only two parameters, an intraband Coulomb interactionU and an interband exchangeJ. WithU=1.8 eV andJ=0.2 eV the self-consistent model solution yields aT=0 moment of about 2.04 µ_B and a Curie-temperature of 1044K. Details of the magnetic behaviour of Fe can be traced back to a striking temperature variation of the quasiparticle density of states. A novel explanation for the experimentally-observed non-collapsing exchange splitting is demonstrated in terms of the temperature-dependent spectral density for wave-vectors near the -point. Typical differences in the magnetic behaviour of Fe and Ni are worked out.     

Mössbauer diffraction measurements on polycrystalline bcc iron

In the early days of Mössbauer spectroscopy, it was demonstrated that coherent scattering of photons emitted by a Mössbauer source can be observed. In spite of the fact that scattering experiments could give information not accessible by the absorption method, they are not widely used. The reasons for this are, on the one hand, experimental difficulties, and on the other hand, the form of the samples, which should be large single crystals in most cases. In this work, we present a Mössbauer diffraction measurement on polycrystalline bcc iron where these problems have been overcome. We demonstrate that using the kinematical theory of gamma-ray diffraction, useful information on the relative orientation of the crystallographic axis to the hyperfine field directions can be subtracted.     

Projected surface energy bands,Shockley surface states,stability and bonding in transition metal aluminides: The example of β′-CoAl

Czechoslovak Journal of Physics -     

Nucleation of bcc iron in ultrathin fcc films

Needle-shaped bcc nucleation centers in fcc films of Fe on Cu(100) are observed by scanning tunneling microscopy. They form virtually without mass transfer and nearly under conservation of volume, which causes a large strain within the nascent bcc grain. The corresponding strain energy almost equals the gain in structural energy, rendering the bcc nucleation very sensitive to any effect influencing this subtle balance. We suggest that modifying the film by straining, alloying, or surface adsorption may inhibit the bcc nucleation and lead to thick metastable fcc films.     

Energetics of small hydrogen-vacancy clusters in bcc iron

Hydrogen may be trapped in voids in iron, leading to undesirable material properties. In this paper, the energetics of small hydrogen-vacancy clusters in body centered cubic iron are investigated. Results from two interatomic potentials are compared. We use molecular dynamics and Monte Carlo methods to find the minimum energy configurations of voids of up to ten vacancies containing up to 50 hydrogen atoms with ratios of hydrogen to vacancy of 10 or less. The formation energies and binding energies of defects to these clusters are calculated. Our results indicate that the hydrogen stabilizes bubbles by causing vacancies to be more tightly bound to clusters, while neighboring irons are less tightly bound. Hydrogen itself becomes less well bound to clusters as the inventory increases. The more physically relevant potential indicates a maximum supported ratio of hydrogen atoms to vacancies of about 4.     

Phonon dispersion of bcc iron to 10 GPa

The phonon dispersion of bcc iron under high pressure to 10 GPa was measured at 300 K by inelastic neutron scattering. Its pressure dependence is surprisingly uniform. Contrary to the behavior found in other bcc elements, there is a lack of any significant pretransitional behavior close to the martensitic bcc-hcp transition which could be related to the Burgers mechanism. This finding confirms predictions by spin-polarized total energy calculations that explain the transition by the effect of pressure on the magnetism of iron. The high pressure frequencies were used to develop a lattice dynamical model from which thermodynamic quantities can be determined at any pressure to 10 GPa.     

The Shockley surface states of electrons in the Kronig-Penney model of a linear chain of atoms joined by alternately strong bonds

The allowed energies of the bond states of electrons in a one-dimensional potential, which is constant along the lines joining the atoms in a chain and has the form of the Diracδ-function in the neighbourhood of the atom, were calculated. The lengths of the bonds alternate. It is found that we get Shockley surface states in a semi-infinite chain, produced from an infinite chain by interrupting the shorter bond. This proves that the results for the given model are qualitatively in agreement with the conclusions reached by the MO LCAO method for an analogical model.     

Atomistic simulation of kink structure on edge dislocation in bcc iron

Based on the general theory of dislocation and kink, we have constructed the three kink models corresponding to the 1/2 （111）{011} and 1/2 （111）{112} edge dislocations （EDs） in bcc Fe using the molecular dynamics method. We found that the geometric structure of a kink depends on the type of ED and the structural energies of the atom sites in the dislocation core region, as well as the geometric symmetry of the dislocation core and the characteristic of the stacking sequence of atomic plane along the dislocation line. The formation energies and widths of the kinks on the 1/2 （111）{011} and 1/2 （111）{112} EDs are calculated, the formation energies are 0.05eV and 0.04eV, and widths are 6.02b and 6.51b, respectively （b is the magnitude of the Burgers vector）. The small formation energies indicate that the formation of kink in the edge dislocation is very easy in bcc Fe.     

Effect of pressure on the magneto-optical properties of bcc and bct iron

We have studied the effect of pressure on the electronic structure of bcc and bct iron within the local spin density approximation (LSDA) for the electronic exchange and correlation. We report calculations of the magneto-optical properties of ferromagnetic iron in the bcc and bct phases using the full potential linearized augmented plane wave (FPLAPW) method as implemented in the WIEN2K code. In both phases, we find two prominent minima in Kerr rotation. In bcc phase, both the calculated Kerr minima shift towards higher energies with increase in pressure while in bct phase, the low energy minimum in Kerr rotation spectra 2 eV becomes less pronounced and the minimum at 7 eV moves towards higher energies on increasing pressure.     

Inelastic quasiparticle lifetimes of the Shockley surface state band on Ni(111)

We present a study of the low-energy quasiparticle lifetimes of the Shockley surface state on the Ni(111) surface with scanning tunnelling spectroscopy. By measuring the coherence length of the decaying standing wave pattern at straight step edges electron and hole lifetimes have been determined. The values of the lifetime measured on this ferromagnetic surface show to be considerable smaller than the values obtained from noble metal surfaces. This is explained by differences in the electron density of states at the Fermi energy but has to include substantial spin-flip scattering. Furthermore hole lifetimes appear to be larger than electron lifetimes with the same excitation energy. Although only results for the majority spin component are presented, a spin-dependent selfenergy is expected.     

Morphological modifications of Ag/Cu(111) probed by photoemission spectroscopy of quantum well states and the Shockley surface state

Epitaxial ultra-thin Ag films grown on Cu(111) have been investigated by angle-resolved photoemission spectroscopy. The thickness dependence of the binding energy for the Shockley surface state at 300 K could be determined accurately in films up to 5 ML thick. Furthermore, we observe drastic changes in the film morphology after annealing to 450 K. Spectral modifications in the shape of the quantum-well states (QWS), characteristic for these ultra-thin silver films, prove that the surface morphology is homogeneous. The photoemission spectra also indicate that the silver film bifurcates to form a film exhibiting two distinct film thicknesses. For all levels of silver coverage, we identify surface regions that are 2 ML thick, while the thickness of the remaining surface depends on the amount of deposited silver. The almost purely Lorentzian line-shape of the spectral features corresponding to the two different surface regions show that both surface areas are atomically flat. PACS 68.55.Jk; 73.20.At; 73.21.Fg; 79.60.Dp     

Binding states of zinc on the polar faces of Zno

The desorption of zinc from cleaved polar faces was investigated in UHV. TDS (calibrated by evaporation of metallic Zn), surface conductivity, LEED and AES were used. The initial sticking coefficient is lower on the Zn face than on the O face, 0.2 and 1 respectively. On both faces two states of adsorption occur. The lower state on the Zn face has an activation energy of 35 kcal/mole(1.5 eV). The corresponding energy on the oxygen face is 16 kcal/mole (0.7 eV). The lower peak is connected with an increase in surface conductivity on both faces. On the Zn face this surface conductivity can be attributed to a surface donor 1.3 eV above the conduction band edge. Above one monolayer the formation of islands and an epitactical growing of a zinc lattice were found.     

Chemisorption of a monolayer of atoms on a bcc metal surface

The change in the density of states due to the adsorption of a monolayer of atoms on the (001) surface of a bcc metal is presented. The substrate is described by the Linear Combination of Atomic Orbitals (LCAO) scheme and the Tight-Binding (TB) approximation, and both the Green's function formalism and the phase shift technique are employed. Each adatom is represented by a single nondegenerate energy level. Two binding sites for the commensurate monolayer are considered: the on-site and the centered fourfold-site. By assuming that screening of the charges on the adatoms is complete within the surface layer of atoms, the selfconsistency condition of satisfying Friedel's sum rule can be met by varying the orbital energies of the adatoms and the surface plane of atoms of the substrate. The changes in the density of states show strongly skewed bonding and antibonding resonances which occur at different energies for the two binding sites even though equal binding strengths are assumed. A comparison with previous single adatom results shows that the shape and position of the bonding resonance are dependent upon adatom coverage.