Possible effects of oxygen in Te-rich Σ3 (112) grain boundaries in CdTe

Using density functional theory calculation, we show that oxygen (O) exhibits an interesting effect in CdTe. The Te atoms with dangling bonds in a Te-rich rich Σ3 (112) grain boundary (GB) create deep gap states due to strong interaction between Te atoms. However, when such a Te atom is substituted by an O atom, the deep gap states can be shifted toward the valence band, making the site no longer a harmful non-radiative recombination center. We find that O atoms prefer energetically substituting these Te atoms and induce significant lattice relaxation due to their smaller atomic size and stronger electronegativity, which effectively reduces the anion–anion interaction. Consequently, the deep gap states are shifted to lower energy regions close to or even below the top of the valence band.     

Benefits of oxygen in CuInSe2 and CuGaSe2 containing Se-rich grain boundaries

Using density functional theory calculation, we show that oxygen (O) exhibits an interesting effect in CuInSe₂ and CuGaSe₂. The Se atoms with dangling bonds in a Se-rich Σ3 (114) grain boundary (GB) create deep gap states due to strong interaction between Se atoms. However, when such a Se atom is substituted by an O atom, the deep gap states can be shifted into valence band, making the site no longer a harmful non-radiative recombination center. We find that O atoms prefer energetically to substitute these Se atoms and induce significant lattice relaxation due to their smaller atomic size and stronger electronegativity, which effectively reduces the anion–anion interaction. Consequently, the deep gap states are shifted to lower energy regions close or even below the top of the valence band.     

Photoionization of the first- and second-row atom hydrides using synchrotron radiation:β measurements for the outer- and inner-valence shells

Experimental results on the valence shell photoionization of argon- and neon-like molecules are reviewed and unpublished results are included. The outer lone-pair orbitals of the hydride secondrow atoms are characterized by a chlorine, sulfur or phosphorus 3p atomic character revealed by the occurrence of a Cooper minimum in the β trend associated with the first valence band in the photoelectron spectra; this atomic behavior is discussed as a function of the hydrogen environment. By comparing the β trends for the main band in the complex inner-valence photoelectron spectra of the first- and second-row atom hydrides we point out a similar behavior which reveals the main “s” atomic character of the inner valence orbital.     

Spherical electron-ion systems in semiclassical approximation: Atoms and atomic clusters

A semiclassical method for calculating the total energy and spatial distribution of electron density in spherically symmetric electron-ion systems is applied to atoms and both solid and hollow atomic clusters. Both exchange-correlation interaction and second-order gradient correction are taken into account. The contribution due to the fourth-order gradient correction is discussed. An expression is proposed for the oscillating correction to the averaged electron density. An expression is obtained for the equilibrium radius of a hollow cluster. The dependence of the equilibrium radius of an endohedral cluster on the valence of the central atom is analyzed.     

Evidence for localizing properties of XPS applied to valence bands

X-ray photoelectron spectroscopy (XPS)-measurements of the valence bands of Cu, Ag and Au have been performed and their integrated intensities have been compared. A model calculation which considers the influence of the x-ray absorption length as well as the electronic escape depth on the obtained intensities was established and applied to the measurements. An additional electron microscopic study on the surface structure of the evaporated samples has been performed. Its influence on the obtained photoelectron yield is discussed. The results support a marked dependence of the integrated valence band intensity on the atomic number. The implications for the interpretation of XPS valence band spectra of alloys are discussed and compared with corresponding x-ray isochromat spectroscopy (XIS)-measurements. Furthermore we deal with the important question whether XPS-as well as XIS-spectra can be described mainly in terms of the electronic band structure or whether atomic features are also present, though both methods are free from participation of core levels. The results are discussed in terms of localizing properties of XPS.     

锂离子电池掺钴正极材料电子结构的DV-Xα研究

采用原子基表示的第一原理赝势方法 ,计算了正极材料LiMn2 O4的电子结构 ,发现LiMn2 O4的价带主要是由Mn(8)和Mn(9)的 3d轨道和O(7)、O(6 )、O(4 )的 2p轨道构成 ,导带主要是由Mn(8)和Mn(9)的 3d轨道和O(7)的 2 p轨道构成 .通过计算Li5Mn7CoO8的电子结构 ,发现在LiMn2 O4中用钴离子取代 16d位锰离子将使电极材料的费米能减小 ,放电电压降低 ;锂离子的净电荷增大 ,锂离子与氧离子的相互作用增强 ,可逆容量降低 ;同时由于价带宽度变窄 ,Co-O键间的相互作用比Mn -O键间的相互作用强 ,所以 ,结构稳定性增加 ,电极循环性能改善 .     

Adsorption on the surface of ionic crystals and the effect of applied electric field

Adsorption of molecules on an ideal surface of ionic crystals and the effect of an external uniform electric field on this process have been investigated using a model Hamiltonian, which takes account of the Coulomb interaction between electrons and atomic cores of the system under consideration, all valence orbitals of the admolecule, as well as their nonorthogonality to the crystal wavefunctions, the substrate band structure. The binding energy as a function of the adsorbate-to-substrate distance is calculated for H₂O and CO on NaCl and MgO (001) surfaces. The main attention is focused on the contributions of admolecule-substrate interaction of various types to the binding energy.     

Observation of spin-selective tunneling in SiGe nanocrystals

Spin-selective tunneling of holes in SiGe nanocrystals contacted by normal-metal leads is reported. The spin selectivity arises from an interplay of the orbital effect of the magnetic field with the strong spin-orbit interaction present in the valence band of the semiconductor. We demonstrate both experimentally and theoretically that spin-selective tunneling in semiconductor nanostructures can be achieved without the use of ferromagnetic contacts. The reported effect, which relies on mixing the light and heavy holes, should be observable in a broad class of quantum-dot systems formed in semiconductors with a degenerate valence band.     

Electron excited Auger line shape study of ion-beam-mixed Pd–Au alloys

The electronic structure of the ion-beam-mixed Pd–Au alloys have been studied using valence band spectra of XPS and electron excited CVV–Auger spectra. To show the relationship between the electronic structure changes and the Auger spectral line shape, the data of the self-convolution of the partially weighted valence band spectra was compared with the Auger spectra of Pd–Au alloys. The Pd–Au alloy is one of the systems which both atomic and band-like contributions are evident in the Auger spectral line shape. Since the self-convolution of PDOS’s relates to the band-like part of Auger spectra, in Pd–Au alloys, the band-like structure in the Auger line shape can be classified by the self-convolution of the partially weighted valence band spectra. Finally, we found that the increase in peak size at ∼80 eV with the increase in Pd content is due to the band-like contribution in the Au N_6,7VV Auger line shape.     

Specific features of the electronic structure of the CeCu<Subscript>6</Subscript>, CePd<Subscript>3</Subscript>, CeSi<Subscript>2</Subscript>, and CeF<Subscript>3</Subscript> systems

The electronic structure of cerium systems, the hybridization of 4 f and outer-shell electrons, and the influence of the position of the localized 4 f level with respect to the Fermi level E _F in the conduction band have been investigated. The CeCu₆, CePd₃, CeSi₂, and CeF₃ systems have been studied using X-ray photoelectron spectroscopy. The densities of states have been calculated by the tight-binding linearized muffin-tin orbital method within the atomic sphere approximation, which takes into account the covalent character of bonds and the nonspherical distribution of the electron density. The results obtained from the calculations of the total density of states are in good agreement with the valence band X-ray photoelectron data for the systems under investigation. It has been shown that the differences in the properties of the cerium systems are determined by the specific features of their electronic structure. A strong interatomic interaction is characteristic of heavy-fermion systems.     

高压下高温超导材料YBa2Cu3O7的电子结构

 本文选用拟合能带的Harrison参数构造紧束缚哈密顿矩阵，采取Recursion方法计算了YBa₂Cu₃O₇晶体在常压下与9 GPa高压下（此时晶格常数压缩3%）的电子结构。讨论了高压对于电子结构的影响。给出了高压下费米面移动，能带展宽和各晶位原子价变化的定量结果。     

Theoretical descriptions of surface state photoelectron spectroscopy

Various approximations which are commonly used in describing photoemission from solids are reviewed. To analyze experimental spectra quantitatively recourse must be had to theoretical calculations of surface states. Over a valence band width of 10 eV these calculations can be accurate to less than 0.5 eV for an assumed atomic surface configuration. For many purposes photoemission spectra may yield more information on allowed atomic configurations than LEED (low-energy electron diffraction) for current levels of sophistication.     

Characterization of electronic structure in dielectric materials by making use of the secondary electron emission

The methodology of characterizing electronic structure in dielectric materials will be presented in detail. Energy distribution of the electrons emitted from dielectric materials by the Auger neutralization of ions is measured and rescaled for Auger self-convolution, which is restructured from the energy distribution of the emitted electrons. The Fourier transform is very effective for obtaining the density of states from the Auger self-convolution. The MgO layer is tested as an example of this new measurement scheme. The density of states in the valence band of the MgO layer is studied by measuring the energy distribution of the emitted electrons for MgO crystal with three different orientations of (111), (100) and (110). The characteristic energy of ?₀ corresponding to the peak density of the states in the band is determined, showing that the (111) orientation has a shallow characteristic energy ?₀ = 7.4 eV, whereas the (110) orientation has a deep characteristic energy ?₀ = 9.6 eV, consistent with the observed coefficient γ of the secondary electron emission for MgO crystal. Electronic structure in new functional nano-films spayed over MgO layer is also characterized. It is therefore demonstrated that secondary electron emission by the Auger neutralization of ions is highly instrumental for the determination of the density of states in the valence band of dielectric materials. This method simultaneously determines the valence band structure and the coefficient γ of the secondary electron emission, which plays the most important role in the electrical breakdown phenomena.     

Influence of the Diagonal and Off-Diagonal Electron–Phonon Interactions on the Formation of Local Polarons and Their Band Structure in Materials with Strong Electron Correlations

For systems with strong electron correlations and strong electron–phonon interaction, we analyze the electron–phonon interaction in local variables. The effects of the mutual influence of electron–electron and electron–phonon interactions that determine the structure of local Hubbard polarons are described. Using a system containing copper–oxygen layers as an example, we consider the competition between the diagonal and off-diagonal interactions of electrons with the breathing mode as the polaron band structure is formed within a corrected formulation of the polaron version of the generalized tight-binding method. The band structure of Hubbard polarons is shown to depend strongly on the temperature due to the excitation of Franck–Condon resonances. For an undoped La₂CuO₄ compound we have described the evolution of the band structure and the spectral function from the hole dispersion in an antiferromagnetic insulator at low temperatures with the valence band maximum at point (π/2, π/2) to the spectrum with the maximum at point (π, π) typical for the paramagnetic phase. The polaron line width at the valence band top and its temperature dependence agree qualitatively with angle-resolved photoemission spectroscopy for undoped cuprates.     

The electronic structure of Be and BeO: benchmark EMS measurements and LCAO calculations

The electronic band structures of Be and BeO have been measured by transmission electron momentum spectroscopy (EMS). The low atomic number of beryllium and the use of ultrathin solid films in these experiments reduce the probability of electron multiple scattering within the sample, resulting in very clean ‘benchmark’ measurements for the EMS technique. Experimental data are compared to tight-binding (LCAO) electronic structure calculations using Hartree–Fock , and local density (LDA-VWN), gradient corrected (PBE) and hybrid (PBE0) density functional theory. Overall, DFT calculations reproduce the EMS data for metallic Be reasonably well. PBE predictions for the valence bandwidth of Be are in excellent agreement with EMS data, provided the calculations employ a large basis set augmented with diffuse functions. For BeO, PBE calculations using a moderately sized basis set are in reasonable agreement with experiment, slightly underestimating the valence bandgap and overestimating the O(2s) and O(2p) bandwidths. The calculations also underestimate the EMS intensity of the O(2p) band around the Γ-point. Simulation of the effects of multiple scattering in the calculated oxide bandstructures do not explain these systematic differences.     

Mixed-valence behaviour of impurities as a mechanism for superconductivity in IV–VI compounds

The properties of PbTe and SnTe doped with elements (indium and thallium), which create localized levels in an allowed band, are discussed from a point of view based on ideas from the theory of mixed-valence systems in the presence of the electron-lattice interaction. The qualitatively different properties of In and Tl in PbTe are attributed to different orders of the valence transition. It is shown that the electron-electron interaction induced by the virtual shift of the position of the localized level can explain the high superconducting transition temperature of PbTe doped with Tl and SnTe doped with In.     

State-specific,many-electron theory of core levels in metals: The 1s binding energy of Be metal

Cluster ΔSCF theory is combined with calculations of atomic electron correlation to predict the 1s binding energy of Be metal as 115.4 eV, in excellent agreement with experiment (115.2–115.6 eV). Upon creation of the 1s hole, the p character of the valence band increases significantly. This explains the existing discrepancy between the experimental solid state fluorescence yield of Be and the theoretical prediction for the atomic state.     

Core-hole screening effects in the initial state of Auger emission across the transition metal series

Supercell method is used to study the relaxation and screening effects on the initial state of the Auger transition in metals. Our consideration is based on the assumption that when a core-hole exists long enough before the Auger transition occurs, the occupied valence states relax to screen the core-hole which results in a redistribution of the valence electrons, in particular within the atom that contains the core-hole. In order to make the interaction between the core-holes sites at different atoms negligible, the real metal is simulated by supercells repeated periodically. In each supercell one atom is considered to have a core-hole and many others not to have one. The electronic states concerned by the Auger transition are calculated by the self-consistent full-potential linearized augmented plane wave (FLAPW) method. Different responses of the local valence band on the site of the core-hole have been shown depending on whether the d-bands are partially or completely filled. According to the final state rule, the screening to the two holes in the local valence band after the Auger transition has also been considered, as examples, for Ni and Cu metals. The result shows that, with the existence of two holes in them, the states of the local valence band of Cu relax to atomic-like impurity states, while the local valence band of Ni changes to a much narrow band at the bottom of the original band. As examples, L₃VV and M₁VV Auger spectral profiles of Cu have been calculated in reasonably good agreement with the experiment.     

Enhanced quadrupole collectivity at N = 40: the case of neutron-rich Fe isotopes

The transition rates for the 2(1)+ states in (62,64,66)Fe were studied using the recoil distance Doppler-shift technique applied to projectile Coulomb excitation reactions. The deduced E2 strengths illustrate the enhanced collectivity of the neutron-rich Fe isotopes up to N = 40. The results are interpreted using the generalized concept of valence proton symmetry which describes the evolution of nuclear structure around N = 40 as governed by the number of valence protons with respect to Z ≈ 30. The trend of collectivity suggested by the experimental data is described by state-of-the-art shell-model calculations with a new effective interaction developed for the fpgd valence space.