Theoretical interpretation of spin-polarized X-ray absorption spectra of Mn in MnP

On the basis of the multiple scattering approach in combination with the spin-polarized self-consistent potential calculation, an interpretation is proposed for the spin-polarized x-ray absorption spectra near the Mn K edge in MnP. The effect of the core vacancy potential on the spectra is analyzed and found to be insignificant. The method used for the calculations allowed the separation of the effect of the dipole transition matrix element on the spectra and the effect of the density of unoccupied electron states. It is shown that the transition matrix element causes an intensity redistribution only near the absorption jump, while the difference in the densities of states is most pronounced in the energy region 35–55 eV away from the main edge and leads to a shift in energy for the spectra corresponding to the two spin directions. The effect of the spin-dependent broadening caused by the dependence of the mean free path (as a function of energy) on the photoelectron spin is studied. It is shown that this factor considerably affects only the intensities of the peaks in the energy region lying within less than 12 eV from the main edge.     

Many body satellite in the photoemission spectra of the heavy rare earths

A narrow feature is reported in the photoemission spectra of the heavy rare earths, Gd, Tb, and Dy on a variety of substrates. This feature is not expected from the initial densities of states. This feature appears to require a density of states at the Fermi energy to exist. We propose that the feature is due to a many electron shakeup process to the unoccupied 4f levels.     

First-principles study of the sulfur K and L2,3 edges of transition metal disulfide monolayers,MS2 (M=Mo,W and Re)

By means of the energy loss near edge structure (ELNES) analysis, the electronic structures of layered transition metal disulfides were studied. In the framework of full potential linearized augmented plane wave method, ELNES spectra of sulfur K and L_2,3 edges of layered MoS₂, WS₂ and ReS₂ have been calculated at magic angle conditions, and compared with those of bulks and the only existing experimental fine structure. Compared to the bulks, the energy differences between the main peaks in sulfur K and L_2,3 edges of monolayers decrease due to the slightly larger bond lengths that it can be used as a fingerprint for monolayers. Sulfur K edges in monolayers include some main features originated from electron transition to p_z (π) and p_x+p_y (σ) states and their hybridization. The overall dispersions of the sulfur L_2,3 edges in all cases are similar to the d-symmetry density of states. The first two features in L_2,3 edge of bulks and monolayers can be attributed to electron transition of sulfur 2p to the both unoccupied 3s-like states of sulfur and 4d states of transition metal atoms. Due to the considerable amount of s states at the energy position of a shoulder like structure in L_2,3 edge of both bulks and monolayers, these structures can be assigned to the sulfur 2p electron transition to unoccupied sulfur 3s states. The other features at higher energies are due to the transition of sulfur 2p electrons to the d-symmetry states of sulfur. In addition, due to the considerable energy band gaps, it seems that the use of core–hole approximation is essential for accurate reproduction of ELNES features of transition metal disulfides.     

Study of the order–disorder transition and martensitic transformation in a Cu–Al–Be alloy by EELS

Changes in 3d states occupancy associated with order–disorder transition and martensitic transformation in a Cu–Al–Be alloy was investigated by electron energy loss spectroscopy (EELS) in both high energy and low energy loss regions. From the high energy loss region, the Cu L_2,3 white-line intensities, which reflect the unoccupied density of states in 3d bands, was measured for three states of the alloy: disordered austenite, ordered austenite and martensite. It was found that the white-line intensity remains the same during order–disorder transition but appears slightly smaller in martensite, indicating that some electrons left Cu 3d bands or some hybridization took place during phase transformation. From the low energy loss region, the optical joint density of states (OJDS) was obtained by Kramers–Kronig analysis. As maxima observed in the OJDS spectra are assigned to interband transitions, these spectra can be used to probe changes in the electronic band structure. The analysis shows that during the martensitic transformation, the peaks positions and relative intensities in the OJDS spectra undergoes noticeable changes, which are associated with interband transitions.     

Double-exchange model for molecule-based magnets

We report a detailed study of a double-exchange model proposed for the molecule-based magnets. The model is applied to a two-dimensional periodic complex made of a transition metal and an organic molecule in which the electronic structure is described by effective d orbitals of the transition metal ion at infinite Hund's coupling limit and the lowest unoccupied molecular orbital of the organic molecule, π^∗. Depending on the average electron density of the organic molecules and various superexchange couplings between metal ions' core spins, magnetic states of the complex are investigated. Performing Monte Carlo calculations on a model Hamiltonian for various electron densities of the organic molecule, the average magnetization and critical magnetic ordering temperatures are determined.     

Unoccupied electronic states in quaterphenyl oligomer films and at the film-gold and film-oxidized silicon interfaces

Thin films of 4-quaterphenyl (4-QP) are thermally deposited in an ultrahigh vacuum on polycrystalline gold and oxidized silicon substrates. In the process of deposition, the structure of unoccupied electron states 5–20 eV above the Fermi level (E _F) and the surface potential are monitored by the method of total current spectroscopy (TCS) using an incident beam of low-energy electrons. During the deposition, the electron work function of the surface changes because of a change in the surface layer composition, reaching a steady-state value of 4.3 ± 0.1 eV at a 4-QP film thickness of 8–10 nm. The density of valence states (DOVS) and the density of unoccupied states (DOUS) in model 4-QP films are calculated using the linearized augmented plane wave method in the generalized gradient approximation of the density functional theory. In the model 4-QP structure, the minimal spacing between carbon atoms of neighboring 4-QP molecules is taken to be 0.4 nm in order that intermolecular interaction can be assumed to be relatively weak, which is observed in disordered 4-QP films. The TCS-measured DOUS and the DOUS predicted theoretically are in good agreement.     

Transmission of electrons through ferromagnetic material and applications to detection of electron spin polarization

The salient features of the total low energy inelastic electron scattering cross section in transition metals are described by a constant term σ₀ plus a term σ_d that is proportional to the number of unoccupied d-orbitals. This simple model predicts that low energy electrons transmitted through a ferromagnetic ultrathin film acquire a transport spin polarization a(χ). Using the ratio σ₀/σ_d as the only adjustable parameter, the model predicts the enhancement of the spin polarization of the low energy cascade electrons as well as a(χ) in reasonable agreement with the existing observations on Fe, Co and Ni. A detector for electron spin polarization P based on the spin dependent transmission of electrons through ferromagnetic material is proposed which should be superior to existing P-detectors by 1–2 orders of magnitude.     

Recent developments in appearance potential spectroscopy

Appearance potential spectroscopy measures the probability for the creation of a hole in an inner atomic shell as a function of electron bombardment energy. The spectrum of excitation thresholds provides a simple means of examining the elemental composition in the surface region of a solid. Near threshold the excitation transitions indirectly probe the unoccupied conduction band states. The localized core state, however, overlaps only part of the conduction band, and the line shapes are thus related to a very local density of states. The interpretation is complicated by broadening introduced by the finite lifetime of the core hole, variations in the magnitude of the atomic matrix elements which suppress some thresholds, and the screening response of the conduction electrons to the suddenly altered core potential. These problems are illustrated by spectra of Th, Nb, Re, SC₂O₃, Ni, and Si surfaces. Distinct spectral characteristics related to crystallographic orientation are reported for nickel single crystals.     

3d 金属电离损失谱研究

本文利用俄歇电子谱仪对Ti,Cr,Ni,Cu等3d金属的电离损失谱作研究,得到它们的空态密度的一些性质:空态密度的最大值位置、空态密度最大值的相对数值和空态密度的宽度。所得结果与理论模型一致。另外,从电离损失谱获得的束缚能值和自旋-轨道分裂值与用XPS所获结果符合良好。电离损失谱是一种研究空态密度的有效方法。 关键词：     

Systematic theoretical investigation of structure and electronic properties of pure copper and lithium doped copper clusters

The pure copper and lithium-doped copper clusters are studied using the unbiased CALYPSO structure searching method and density function theory to understand the evolution of various structure and electronic properties. Theoretical results show the growth behaviours of doped clusters are organised as follows: Li capped Cu_n clusters or Li substituted Cu_n+1 clusters as well as Cu capped Cu_n-1Li clusters. Moreover, the lowest energy structures of Cu_nLi favour planar structures for n ≤ 3 and three-dimensional structures for n = 4–12. In addition, the calculated averaged binding energies, fragmentation energies and second-order difference of energies exhibit obvious odd–even alternations as cluster size increasing. At last, the highest occupied-lowest unoccupied molecular orbital gaps, molecular orbital energy, magnetic property, natural population analysis, natural electron configurations, electrostatic potential, electron density difference, Infrared and Raman spectra and density of states are also, respectively, operative for characterising and rationalising the electronic properties of doped clusters.     

Energy bands and electron densities of Li3N

Self-consistent band-structure calculations on the fast ionic conductor lithium nitride are performed by means of the linearized augmented plane wave (LAPW) method within the local density formalism. The corresponding density of states is decomposed into local (inside spheres), partial (l-like) and symmetry (p _x p _y ;p _z ) components from which an only very small covalent contribution to the bonding in Li₃N can be deduced. Electron density maps reveal Li₃N to be highly ionic (near Li⁺ and N^3–). A simple Watson model, although a good first approximation, cannot account for all details. For instance a remarkable non-spherical electrons density is found around N which may explain the high electric field gradient experimentally observed on this site; furthermore a reduced electron density around the Li-sites appears in contrast to a simple supper-possition of N^3– ionic densities. However, calculated x-ray structure factors and difference electron densities are in good qualitative agreement with recent x-ray diffraction experiments.This work has been supported by the Hochschuljubiläumsstiftung der Stadt Wien. All calculations were carried out at the Rechenzentrum der Technischen Universität Wien     

Conductivity-dependent cathodoluminescence in BaTiO3, SrTiO3 and TiO2

It is reported that similar cathodoluminescence spectra are excited by an electron beam striking BaTiO₃, SrTiO₃ and TiO₂ ceramics at room temperature. The energy location of the luminescence bands does not depend on various doping or reduction treatments. The luminescence intensity increases with the electron beam current as well as with the conduction electron density. The luminescence is interpreted as a fundamental transition of local character in the TiO₆ octahedron; the conduction electrons localized at the Ti sites in polaron states recombine with the 0–2p valence electron defects. The shape and energy location of the luminescence spectra are qualitatively in accordance with an explanation in terms of a configuration coordinate model.     

Superconductivity in ultrathin films I. Transition temperatures of amorphous Bi and Ga

Superconducting transition temperatures (T _c) and electron tunneling characteristics have been measured on amorphous, vapour quenched films of Ga and Bi in the thickness range 3 to 50 nm. TheT _c's are depressed and the tunnel densities of states are smeared as compared to bulk superconductors. A model considering the proximity effect between an extremely thin non-superconducting sheath (presumably due to the decrease of electron concentration at the surfaces) and a remaining bulk superconducting part gives good agreement withT _c measurements, while the predicted tunnel density of states is only in qualitative correspondence with experiments.     

Tuning field emission properties of boron nanocones with catalyst concentration

Single crystalline boron nanocones are prepared by using a simple spin spread method in which Fe 3 O 4 nanoparticles are pre-manipulated on Si(111) to form catalyst patterns of different densities.The density of boron nanocones can be tuned by changing the concentration of catalyst nanoparticles.High-resolution transmission electron microscopy analysis shows that the boron nanocone has a β-tetragonal structure with good crystallization.The field emission behaviour is optimal when the spacing distance is close to the nanocone length,which indicates that this simple spin spread method has great potential applications in electron emission nanodevices.     

First principles study on the charge density and the bulk modulus of the transition metals and their carbides and nitrides

A first principles study of the electronic properties and bulk modulus （B0） of the fcc and bcc transition metals, transition metal carbides and nitrides is presented. The calculations were performed by plane-wave pseudopotential method in the framework of the density functional theory with local density approximation. The density of states and the valence charge densities of these solids are plotted. The results show that B0 does not vary monotonically when the number of the valence d electrons increases. B0 reaches a maximum and then decreases for each of the four sorts of solids. It is related to the occupation of the bonding and anti-bonding states in the solid. The value of the valence charge density at the midpoint between the two nearest metal atoms tends to be proportional to B0.     

Real‐space multiple‐scattering Hubbard model calculations for d‐ and f‐state materials

Calculations are presented of the electronic structure and X‐ray spectra of materials with correlated d‐ and f‐electron states based on the Hubbard model, a real‐space multiple‐scattering formalism and a rotationally invariant local density approximation. Values of the Hubbard parameter are calculated ab initio using the constrained random‐phase approximation. The combination of the real‐space Green's function with Hubbard model corrections provides an efficient approach to describe localized correlated electron states in these systems, and their effect on core‐level X‐ray spectra. Results are presented for the projected density of states and X‐ray absorption spectra for transition metal‐ and lanthanide‐oxides. Results are found to be in good agreement with experiment.     

Theory of valley-splitting without effective-mass approximation

A new method for determining electron states in a crystal with an external potential is proposed. It is applied to the n-inversion layer of Si(001)/SiO₂. The electron densities of the states show oscillations due to the super- position of Bloch waves from different valleys. As a function of the position of the interface there is a continuous transition from states described within the effective-mass approximation of Sham and Nakayama to surface states in the band gap.     

Electronic structure and binding mechanism of Cu2O

A self-consistent LAPW band structure calculation of Cu₂O is presented. Total and partial densities of states and electron densities were calculated and are used to give an interpretation of chemical bonding. It is found that there are significant deviations from a simple ionic picture due to a depletion of the valence band of Cu-3d electrons leading to a non-spherical charge density around Cu. A critical discussion of theoretical and experimental work on Cu₂O is given.     

The genesis of energy bands formed by sublattice states in alkaline-earth metal oxides and sulfides

The self-consistent electron energy band spectra of crystals and charged sublattices of alkaline-earth metal oxides and sulfides are calculated in the framework of the density functional theory within the pseudopotential approximation in the basis set of localized orbitals. The charge states of sublattices (such as neutral sublattices, empty metal sublattices, and doubly charged anion sublattices) are analyzed with due regard for the electrical neutrality of the crystal. It is demonstrated that the valence bands of the studied crystals are very similar to the valence bands of the doubly charged anion sublattices. The distributions of the valence electron densities of the crystals are virtually identical to those of the anion sublattices. The lower conduction bands of the crystals and doubly charged anion sublattices also almost coincide with each other for MgO and MgS but differ substantially for CaO and CaS. This is associated with the difference between the contributions from the anions and cations to the conduction band of the crystals. It is found that these contributions depend on the relative energy positions of p and d unoccupied states.

     

Crystal and electronic structure of solid C76

The crystal and electronic structure of solidC ₇₆ has been studied using transmission electron microscopy and electron energy-loss spectroscopy in transmission. C₇₆ forms a close packed structure with an average facecentred cubic symmetry. From valence band and core electron excitations information on the dielectric function and the unoccupied density of states has been obtained.