Interplay of negative pressure and hydrogen chemical effects in CeRhSn from first principles

Investigations within the local spin density functional theory (LSDF) of the intermetallic hydride system CeRhSnH_x were carried out for discrete model compositions in the range 0.33 ≤x_H ≤ 1.33 with the purpose of assessing the change of the cerium valence state in the neighborhood of the experimental hydride composition, CeRhSnH_0.8. In agreement with experiment, the analyses of the electronic and magnetic structures and of the chemical bonding properties point to trivalent cerium for 1 ≤x_H ≤ 1.33. In contrast, for lower hydrogen amounts the hydride system stays in an intermediate-valent state for cerium, like in CeRhSn. The influence of the insertion of hydrogen is addressed from both the volume expansion and chemical bonding effects. The latter are found to have the main influence on the change of Ce valence character. Spin polarized calculations point to a finite magnetic moment carried by the Ce 4f states; its magnitude increases with x_H in the range 1 ≤x_H ≤ 1.33.     

Evolution from a non-Fermi liquid Kondo lattice to intermediate valence behaviour in CeRhSn(1-x)In(x)

We present investigations of the magnetic and electric transport properties, specific heat, and electronic structure of the intermetallic and strongly correlated system of CeRhSn(1-x)In(x) compounds. The main goal of this paper is to determine the hybridization energy between the f electron and conduction electron states, V(cf), and its influence on the ground state properties of the system. The complementary experimental data are discussed on the basis of the Anderson model for a periodic Kondo lattice. CeRhSn is known as a non-Fermi liquid, while CeRhIn is a valence fluctuating system. We discuss the ground state properties of CeRhSn(1-x)In(x) and compare the results with those obtained for the doped Ce-based Kondo insulators.     

Magnetic properties and electronic structure of GdNi4Si compound

Electronic structure of the ternary GdNi₄Si compound, crystallizing in hexagonal CaCu₅ structure (P6/mmm space group) was studied by magnetic measurements, X-ray photoelectron spectroscopy (XPS) and ab initio calculations. Core levels and valence band were investigated. The valence band of the XPS spectra is determined mainly by the Ni(3d) and Gd(4f) bands. The peaks’ positions are in good agreement with binding energies of a metallic gadolinium and nickel. The experimental valence band spectrum as well as the calculated density of states exhibit the domination of the Ni(3d) states in region from −4 eV to the Fermi level.     

High-resolution resonant photoemission study of the 4f states in a typical Kondo system: CePd3

We exploited resonant photoemission at the Ce absorption edge to investigate the Ce 4f states in . High resolution spectra reveal, near the Fermi level, the characteristic fine structure of intermediate valence Ce compounds. The spectral lineshape is consistent with the typical “Kondo” character of CePd, but the prominent ionization peak is found at the unusually low binding energy of 1 eV. We briefly discuss the implications of these observations. Received: 13 October 1997 / Accepted: 21 January 1998     

Electronic structure of Ce-pnictides

High-resolution x-ray photoemission has been used to study the electronic structure of the Ce-pnictides (CeN, CeP, CeAs and CeSb). This series of isostructural compounds allows us to follow the evolution of the 4f level as the distance between Ce atoms varies. Core level spectra show clearly that the 4f state is localized in all the compounds. In the valence band region, the width of the 4f peak is strongly influenced by the energy overlap with the extended states originating from anion p states. The spectra of CeN reveal the existence of a mixed configuration.     

Band structure calculations on the layered compounds FeGa2S4 and NiGa2S4

For the compounds FeGa₂S₄ and NiGa₂S₄ band structure calculations have been performed by the ab initio plane wave pseudo-potential method. The valence charge density distribution points to an ionic type of chemical bonding between the transition metal atoms and the ligand atoms. Two models for the pseudo-potentials are used to calculate the band structures: (a) only s and p electrons and (b) also the d-shells of the transition metal atoms are included in the pseudo-potentials. The differences between these two cases of band structures are discussed. Energy gap formation peculiarities are analysed for both crystals. Zak's elementary energy band concept is demonstrated for the energy spectra of the considered crystals.     

The electronic structure of cobalt phthalocyanine

The electronic structure and morphology of organic semiconducting cobalt-phtalocyanine (CoPc) films in situ prepared on the Au(001)-5×20 superstructure have been studied by a combination of experimental and theoretical work. The CoPc molecular film was characterized by photoemission spectroscopy (PES, valence band and core-level). The experimental results were simulated and have been explained in the framework of density functional theory (DFT) calculations. The C 1s and N 1s core level spectra were analyzed by taking into account the fact that both types of atoms have different nonequivalent positions in the molecule. And finally, the experimentally obtained electronic valence band structure of CoPc is in very good agreement with ab initio density of state results, allowing a detailed site-specific insight into the system.     

Electronic structure,optical dielectric constant and born effective charge of EuAlO3

EuAlO₃ (EAO) is synthesized by the sol–gel process. The Rietveld refinement of the X-ray diffraction data shows that the material has orthorhombic structure with Pbnm space group. The density functional theory calculations are initiated with the experimental lattice parameters. The full potential linearized augmented plane wave method and projector augmented wave method are used to investigate the ground state properties of EAO. An indirect band gap of 1.8 eV is observed with the valence band maximum at the Γ point and the conduction band minimum at the R point. The X-ray photoemission spectroscopy (XPS) spectra of EAO are obtained in the energy window of 0–1000 eV. Using the electronic density of states, the valence band (VB) spectrum of EAO is generated and compared with the observed VB-XPS spectrum. The optical dielectric constant and the refractive index of the material are calculated for the photon energy radiation. The optical properties show a considerable anisotropy in the material. The Born effective charge of various elements and the dielectric tensor of EAO have been calculated.     

5f electron localization in metallic UPd3

We have determined the electronic structure of UPd₃ by means of XPS and BIS experiments. The core level line shapes and the valence band spectra of occupied and empty states clearly reveal the localized character of the 5f electrons in this actinide compound. From these spectra their Coulomb correlation energy is found to be about 2 eV.     

Influence of vacancies on the electronic structure of Co ZrSn Heusler alloys

The electronic structure of the Co_2-xZrSn Heusler alloys has been studied by X-ray photoelectron spectroscopy (XPS). XPS valence band spectra can be compared with ab initio electronic structure calculations using the linearized muffin-tin orbital (LMTO) method. The calculated magnetic moments per Co atom agree well with the moments obtained from experiment. The LMTO calculations also show the energy shifts of the Co, Zr and Sn valence electron states towards the Fermi level when the concentration of vacancies increases in these alloys. Received 9 March 1999 and Received in final form 6 May 1999     

Electronic structure and self-assembling processes in platinum metalloporphyrins: photoemission and AFM studies

The main goal of this paper is to investigate the electronic structure of valence band and core levels as well as surface topography of pristine tetraphenylporphyrin and Pt-based compounds Pt-TPP(p-COOH₃)₄, Pt-TPP(m-OCH₃)₄, PtCl₂-TPP(m-OCH₃)₄ thin films. The electronic structure of various Pt-based metalloporphyrins which were investigated in dependence on their chemical structure and spectra were measured by high-resolution X-ray photoelectron spectroscopy (XPS) of valence band and Pt4f, Pt4d, C1s, O1s, N1s core levels. Results of atomic force microscopy (AFM) studies of topography and self-assembling processes in thin films of porphyrines are presented and discussed.     

Single impurity Anderson model versus density functional theory for describing Ce L3 x-ray absorption spectra of CeFe2: resolution of a recent controversy

We resolved a recent controversy on the structure of the Ce L(3) x-ray absorption spectra (XAS) of CeFe(2); i.e., which of the single impurity Anderson model (SIAM) and the first-principles band calculations based on the density-functional theory (DFT) describes more appropriately the Ce 4f states and their contribution to the Ce L(3) XAS? For this purpose, we examined the core-hole effect in Ce L(3) XAS as an application of our new method taking advantage of resonant x-ray emission spectroscopy. Our result clearly shows that the Ce L(3) XAS structure is caused by the mixed valence 4f character revealed by the core-hole potential effect as indicated by SIAM, but denies the possibility that the L(3) XAS structure is caused by the 5d band structure with a very small core-hole effect as predicted by band calculations based on DFT.     

Electronic structure and magnetic properties of Gd3Co11B4 compound

The electronic structure of hexagonal Gd₃Co₁₁B₄ compound has been studied by X-ray photoemission spectroscopy (XPS) and ab initio self-consistent tight binding linear muffin tin orbital (TB LMTO) method. We have found a good agreement between the experimental XPS valence band spectra and theoretical LMTO calculations. Results showed that the Gd₃Co₁₁B₄ compound is ferrimagnetic with the calculated total magnetic moment M=14.29 μ_B/f.u. The values of the magnetic moments on Co atoms strongly depend on the local environment. We have also compared the electronic structure and magnetic properties of Gd₃Co₁₁B₄ compound with those of Nd₃Co₁₁B₄ compound.     

Study of the atomic and electronic structures of liquid gold

The electronic and atomic structures of liquid gold has been studied theoretically and experimentally using X-ray photoelectron spectroscopy (XPS) and a combination of classical molecular dynamics and ab initio band calculations. The results obtained showed good agreement between the XPS data and the results of calculations of the total density of states. It is shown that the bonding of atoms in liquid gold clusters is covalent.     

Photoemission of LaI2 and CeI2

The electronic structure of the layered compounds LaI₂ and CeI₂ was investigated by photoemission and electron energy loss spectroscopy. From the experimental results we are able to confirm the metallic nature of these compounds, and by using photon energy dependent measurements of the valence band we can identify the orbital character of the conduction band as essentially 5d¹-like. A detailed analysis of the Ce 3d and 4f spectra yields a remarkably small 4f-5d hybridization strength, almost completely decoupling the f-electron from the conduction band, which makes CeI₂ a somewhat unusual system compared to other metallic Ce compounds. Band structure calculations by Jepsen and Andersen [1] confirm these experimental results.     

Electronic structure of β-RbNd(MoO4)2 by XPS and XES

β-RbNd(MoO₄)₂ microplates have been prepared by the multistage solid state synthesis method. The phase composition and micromorphology of the final product have been evaluated by XRD and SEM methods. The electronic structure of β-RbNd(MoO₄)₂ molybdate has been studied employing the X-ray photoelectron spectroscopy (XPS) and X-ray emission spectroscopy (XES). For the molybdate, the XPS core-level and valence-band spectra, as well as XES bands representing energy distribution of the Mo 4d- and O 2p-like states, have been measured. It has been established that the O 2p-like states contribute mainly to the upper portion of the valence band with also significant contributions throughout the whole valence-band region. The Mo 4d-like states contribute mainly to a lower valence band portion.     

Anisotropic tight-binding model applied to zigzag ultra-small nanotubes

A single-wall carbon nanotube (SWCNT) can be visualized as a graphene rolled into a cylinder. Tight-binding band structure calculations, with hopping between nearest-neighbor π orbitals only (NNTB), established rules by which both the mode in which the graphene is rolled up and the diameter determine whether the SWCNT is a metal or a semiconductor. However, when the diameter of the SWCNT is ultra-small its large curvature results in the breakage of these rules. In this work, we studied zigzag (n, 0) SWCNTs with diameters smaller than 0.7 nm using a π orbital-only tight-binding model including anisotropy in the hopping between next-nearest-neighbor sites (ANNNTB). Band overlaps were found in the electronic band structures of the zigzag SWCNTs for n=3, 4, 5, and 6, indicating that they are metals. The reason why the band structures of armchair and chiral SWCNTs are less affected by curvature effects becomes clear with the ANNNTB model, as does the reason why non-degenerate states cause band overlaps of the zigzag SWCNTs for n=3, 4, 5, and 6. Our results show that a π orbital-only tight-binding model is able to describe both the band overlaps and gaps obtained by ab initio calculations for zigzag SWCNTs.     

Effect of a finite conduction-band width on XMCD spectra at the L2,3 absorption edges of mixed-valence Ce and Yb compounds in high magnetic fields

Effect of a finite conduction-band width is studied in detail on the spectra of X-ray absorption spectroscopy (XAS) and its X-ray magnetic circular dichroism (XMCD) at the L_2,3 absorption edges of mixed valence Ce and Yb compounds in high magnetic fields. Calculations are made with an extended single impurity Anderson model and within the leading term approximation in the 1/N_f expansion method, where N_f is the degeneracy of the 4f states. It is shown that a model with a vanishing conduction-band width is applicable, as an approximation method, to the calculation of XAS and XMCD spectra for realistic systems with a finite conduction-band width, if the values of the 4f level and the hybridization strength are renormalized appropriately. This justifies the previous calculations on general features of high-magnetic-field XAS and XMCD spectra with zero conduction-band width. At the same time, it is also shown that for more realistic calculations of high-magnetic-field XMCD spectra of some specific mixed-valence Ce and Yb compounds, the present theory with a finite conduction-band width is more appropriate.