Electronic structure of CeRhX (X = Sn,In)

Electronic structure of the compounds CeRhIn and CeRhSn have been studied by the X-ray photoemission spectroscopy (XPS) and ab initio band structure calculations. CeRhSn shows the non-Fermi liquid characteristics at low temperatures, while CeRhIn exhibits a Fermi-liquid ground state. At ambient temperature the XPS data reveal an intermediate valence state of Ce ions in both systems. The Ce core-level XPS spectra are very similar and indicate the strong coupling of the Ce 4f and the conduction band states (Δ ≈ 100 meV). The valence band spectra we interpret with the help of ab initio calculations as well as using the results for the reference compounds LaRhIn and LaRhSn. The comparative analysis of the theoretical band structures and charge density plots reveal the changes in chemical bonding and the hybridization between the Ce 4f and the other valence states introduced by the replacement of In by Sn atoms. The more covalent character of the chemical bonding in the stannides is in line with the smaller thermal expansion. Finally, for CeRhIn we found a typical temperature dependence of the crystal lattice, while CeRhSn shows distinct anomaly at about 120 K, presumably related to the change in planar Ce–Rh bonds.     

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.     

Ab initio studies on magnetism and hybridization of the ternary germanide

We perform a theoretical investigation on the magnetism and orbital hybridization in ternary germanide Ce₃Ni₂Ge₇ using the full-potential linearized augmented plane wave method (FP_LAPW) based on the density functional theory (DFT). The calculation with local spin density approximation (LSDA) predicts that there are two states for the Ce atoms due to the different environment: one (Ce₁) is near the nonmagnetic state and the other (Ce₂) is localized and magnetic. The orbital hybridization plays a key role in determining the state of Ce. On adding on-site Coulomb potential to the localized Ce₂-4f orbit, the magnetic moment obtained from our calculation fits well with the experimental value.     

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     

Magnetism and electronic structure of the intermetallic compound Ce5CuBi3

We have studied the electronic structure as well as magnetic, electronic transport and thermodynamic properties of the intermetallic compound Ce₅CuBi₃. It was found that Ce₅CuBi₃ undergoes three successive phase transitions at 25?K, 13.7?K and 3.5?K. We attribute the multiple magnetic phase transition to be associated with the two non-equivalent magnetic sublattices of the magnetic Ce ions. The investigated compound is characterized by an enhanced ratio C_p /T at 2?K, which may be interpreted as being due to the nearness of the 4f-level to the Fermi level and some contribution of magnon excitation. The core-level photoemission spectra indicate that Ce ions in Ce₅CuBi₃ are very close to trivalent which is consistent with the magnetic susceptibility data. The calculated band structures using the scalar-relativistic linear muffin-tin orbital method in the atomic sphere approximation and the all-electron full potential linear augmented plane wave plus local orbitals method have been performed for the non-magnetic ground state and as well as for collinear ferromagnetic and ferrimagnetic spin alignments. The largest stabilization energy is found in the case of a ferromagnetic structure. The calculated moments on the two sites of the Ce atoms are in agreement with the experimental value (0.93?μ _B /Ce). The calculations predict that the studied compound has a pseudogap in the DOS curve. Analysis of the partial DOS suggests some differences in hybridization strengths between the Ce-Bi and Ce-Cu orbitals.     

Complex magnetic behavior in Ce5Rh4Sn10 doped with La

Ce₅Rh₄Sn₁₀ is known as a heavy-fermion antiferromagnet with magnetic-ordering temperature T _N2?=?4.3?K. We report a new antiferromagnetic phase transition at T _N1?=?1.4?K. In the series of Ce_1?x La _x Rh₄Sn₁₀ compounds both magnetic phase transitions at T _N1 and T _N2 shift towards lower temperatures. For Ce₃La₂Rh₄Sn₁₀ and Ce_3.5La_1.5Rh₄Sn₁₀ we found only one transition. In the temperature region T _N1<T<T _N2, the magnetization M measured as a function of magnetic field H exhibits a large jump at very low fields of ～0.03?T with a very small hysteresis loop. This abnormal behavior could be due to spin-flip transitions. Thermodynamical properties of the series of Ce_1?x La _x Rh₄Sn₁₀ compounds are discussed in terms of the antiferromagnetic Kondo lattice.     

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.     

Magnetic structure of the ternary germanide Ce3Ni2Ge7

The ternary germanide Ce₃Ni₂Ge₇ has been studied by means of neutron powder diffraction and Ce L_III X-ray absorption (XAS). This compound which orders antiferromagnetically below T_N=7.2(2) K, crystallizes in the orthorhombic (Cmmm space group) La₃Co₂Sn₇-type structure where Ce atoms occupying two inequivalent crystallographic sites: Ce1 at 2d site and Ce2 at 4i site. Below T_N, the antiferromagnetic structure of Ce₃Ni₂Ge₇ is collinear but only the Ce2 atoms carry a magnetic moment (1.98(2) μ_B at 1.4 K). The absence of ordered magnetic moment on Ce1 atoms can be correlated to the average valence v=3.03(1), determined by X-ray absorption spectroscopy, suggesting an intermediate valence state of cerium in the 2d site.     

The crystal structure of SnYb3Rh4Sn12, a new ternary superconducting stannide

The crystal structure of superconducting SnYb₃Rh₄Sn₁₂ has been determined from single-crystal X-ray diffraction data. This compound is cubic, space group Pm3n, $\text{a}{}_{\mathrm{o}}\text{= 9.676}\text{A}\text{?}$ (1) and has two formulae per unit cell. The structure was solved from Patterson and subsequent Fourier synthesis. The least squares refinement was based on 375 independent reflections. The final R and wR factors were 0.015 and 0.014, respectively. The two Sn(1) atoms occupy the 2a (000) positions, the six Yb atoms the 6d ($\text{1}\text{4}$$\text{1}\text{2}$ 0) positions, the eight Rh atoms the 8e ($\text{1}\text{4}$$\text{1}\text{4}$$\text{1}\text{4}$) positions and the twenty-four Sn(2) atoms the 24k (Oyz) positions (y ～ 0.31, z ～ 0.15). The Sn(2) atoms form a tridimensional array of corner-sharing trigonal prisms whose centers are occupied by the rhodium atoms. The Sn(1) and the Yb atoms occupy the icosahedral and cuboctahedral holes of this array, respectively. They form a sublattice which has the arrangement found in the structure of the A15 compounds. The structure of SnYb₃Rh₄Sn₁₂ can be described as containing two interpenetrated structures, namely Yb₃Sn and RhSn₃, or as having an A15 arrangement of clusters of atoms such as (SnSn₁₂) and (YbSn₁₂). These clusters are bound together by face-sharing among them; and by the rhodium atoms. An analogy is drawn between SnYb₃Rh₄Sn₁₂ and the perovskite-like ternary oxides A′A″₃B₄O₁₂.     

Photoluminescence of SrGa2S4:Sn,Re(=Ce, Gd) phosphors

The photoluminescence (PL) spectra, PL excitation spectra, color coordinates, and X-ray diffraction spectra are reported for SrGa₂S₄:Sn,Re(=Ce and Gd, respectively) phosphors. By mixing SrGa₂S₄:Sn,Ce phosphors with different Ce³⁺ concentrations, white emissions can be obtained under the excitation of a 340-nm UV LED. Emissions in the green to yellow color range can be obtained from SrGa₂S₄:Sn,Gd phosphors. The rare earth ions enhance the green emission band, which peaks at 534 nm, instead of the yellow one. The origin of this enhancement is discussed. The resonant energy transfer rates are estimated in the cases from Ce³⁺ to the green and yellow centers of Sn²⁺ and between the yellow centers and the green centers.     

Study of Hyperfine Fields in CeIn3 by Electronic Structure Calculations

Electronic band structure calculations for the CeIn₃ compound utilizing the full potential linearized augmented plane waves method were performed with the aim to compute the hyperfine fields acting on Ce and In atoms. The latter are found to be in reasonable agreement with the values measured at low temperatures. The 4f orbital contribution dominates the magnetic hyperfine field at Ce ions while the contact field is negligible due to an almost complete cancellation of valence and core contributions. A non-zero magnetic hyperfine field appears at In sites due to the spin-polarization of the 5p sub-shells through the hybridization with the extended 6s, 6p and 5d Ce states which, in turn, are spin-polarized by the Ce 4f states. No net magnetic moment at In is observed since the sum of its 5p sub-shell spins is zero. The 5p shell of In is responsible for the presence of an electric field gradient at In nuclei. This revised version was published online in September 2006 with corrections to the Cover Date.     

Influence of local environment on electronic properties of Co atoms in the Tm3Co11B4 compound

The electronic structure of the Tm₃Co₁₁B₄ compound has been studied by X-ray photoemission spectroscopy and ab initio self-consistent tight binding linear muffin tin orbital (TB LMTO) method. This compound crystallizes in the hexagonal Ce₃Co₁₁B₄-type structure (P6/mmm). We have found a good agreement between the experimental XPS valence band spectra and theoretical ab initio calculations. The calculated total magnetic moment is equal to 13.635 μ_B/f.u. The magnetic moments on the Co atoms are antiparallel to the moments of the Tm atoms. Their values are depended on the local environment, especially on the number of the Co neighbors. The theoretical results are compared with other calculations, saturation magnetization measurements as well as neutron diffraction data for R₃Co₁₁B₄ (R=Y, Nd, Gd, Tb).     

A resonant photoemission study of the Ce and Ce-oxide/Pd(1 1 1) interfaces

We have investigated the Ce 4f electronic states in the Ce/Pd(1 1 1) and Ce-oxide/Pd(1 1 1) systems, using resonant photoemission (Ce 4d → 4f transitions), and XPS to understand Pd-Ce interactions in ultra thin layers of cerium and ceria deposited on Pd(1 1 1). Cerium deposited on Pd(1 1 1) at room temperature forms surface Ce-Pd alloys with Ce rich character, while a Pd rich Ce-Pd alloy is formed by heating to 700 °C. A modification of the chemical state of Ce can also be seen after oxygen exposure. RPES provides evidence that Ce-oxide layers deposited on Pd(1 1 1) have a CeO₂ (Ce⁴⁺) character, however a net contribution of the Ce³⁺ states is also revealed. The Ce³⁺ states have surface character and are accompanied by oxygen vacancies. Heating to 600 °C causes Ce-oxide reduction. A significant shift of Pd 4d-derived states, induced by Pd 4d and Ce 4f hybridization, was observed. The resonant features in the valence band corresponding to Ce⁴⁺, Ce³⁺ and Ce⁰ states have been investigated for various Pd−Ce(CeO_x) coverages.     

Electronic structure of ZrTiO4 and HfTiO4: Self-consistent cluster calculations and X-ray spectroscopy studies

Total and partial densities of states of the constituent atoms of ZrTiO₄ and HfTiO₄ titanates have been calculated using a self-consistent cluster method as incorporated in the FEFF8 code. The calculations reveal the similarity of the electronic structure of both titanates and indicate that the valence band of the compounds under consideration is dominated by contributions of O 2p states. These states contribute throughout the whole valence-band region; however their maximum contributions occur in the upper portion of the band. Other significant contributors in the valence-band region are Ti 3d and Zr 4d states in ZrTiO₄ and Ti 3d and Hf 5d states in HfTiO₄. All the above d-like states contribute throughout the whole valence-band region of the titanates; however maximum contributions of the Ti 3d states occur in the upper portion, whilst those of the Zr 4d (Hf 5d) states are in the central portions of the valence band. The FEFF8 calculations render that the bottom of the conduction band of ZrTiO₄ and HfTiO₄ is dominated by contributions of Ti 3d^? states, with also smaller contributions of Zr 4d^?/Hf 5d^? and O 2p^? states. To verify the above FEFF8 data, the X-ray emission bands, representing the energy distributions of mainly O 2p, Ti 3d and Zr 4d states, were measured and compared on a common energy scale. These experimental data are found to be in agreement with the theoretical FEFF8 results for the electronic structure of ZrTiO₄ and HfTiO₄ titanates. Additionally, X-ray photoelectron valence-band and core-level spectra were recorded for the constituent atoms of the titanates under study.     

Electronic properties of anatase TiO2 doped by lanthanides: A DFT+U study

The effects of mono-doping of 4f lanthanides with and without oxygen vacancy defect on the electronic structures of anatase TiO₂ have been studied by first-principles calculations with DFT+U (DFT with Hubbard U correction) to treat the strong correlation of Ti 3d electrons and lanthanides 4f electrons. Our results revealed that dopant Ce is easy to incorporate into the TiO₂ host by substituting Ti due to its lower substitutional energy (∼−2.0 eV), but the band gap of the system almost keeps intact after doping. The Ce 4f states are located at the bottom of conduction band, which mainly originates from Ti 3d states. The magnetic moment of doped Ce disappears due to electron transfer from Ce to the nearest O atoms. For Pr and Gd doping, their substitutional energies are similar and close to zero, indicating that both of them may also incorporate into the TiO₂ host. For Pr doping, some 4f spin-down states are located next to the bottom of the conduction band and narrow the band gap of the doping system. However, for Gd doping, the 4f states are located in deep valence band and there is no intermediate band in the band gap. The magnetic moment of dopant Gd is close to the value of isolated Gd atom (∼7 μB), indicating no overlapping between Gd 4f with other orbitals. For Eu, it is hard to incorporate into the TiO₂ host due to its very higher substitutional energy. The results also indicated that oxygen vacancy defect may enhance the adsorption of the visible light in Ln-doped TiO₂ system.     

双原子填充式skutterudite化合物的结构及X射线光电子能谱分析

用高温熔融、淬火、扩散退火结合放电等离子烧结(SPS)法合成了Ca和Ce复合填充的单相Ca_mCe_nFe_xCo_4-xSb₁₂(m=0.17—0.27，n=0.05—0.25，x=1.5)化合物，并结合Rietveld结构解析以及X射线光电子能谱(XPS)分析研究了两种原子复合填充skutterudite化合物的结构与填充状态.Rietveld结构解析表明，Ca_mCe_nFe_1.5Co_2.5Sb₁₂化合物具有skutterudite结构，Ca和Ce原子填充到了Sb的二十面体空洞中，填充原子热振动参数B_Ca/Ce远大于框架原子的热振动参数B_Fe/Co和B_Sb.XPS元素窄区谱分析结果表明，Sb原子在结构中有五种化学状态，每种化学状态的相对含量主要由总填充分数决定，填充原子Ca在Sb的二十面体空洞出现概率有三种可能，但在中心位置出现的概率最大. 关键词： skutterudite化合物 双原子复合填充 结构 X射线光电子能谱分析     

Ab initio studies on the electronic structure of CeSi5

We investigated the electronic properties of CeSi₅ by band structure calculation based on the density functional theory within LDA, LDA+U, and fully relativistic schemes. The calculated band structure scheme shows that the spin-orbit coupling splits the Ce 4f states into three manifolds. When the on-site Coulomb potential is added to the Ce-derived 4f orbitals, the degeneracy between the f orbitals would be lifted and they are split into lower Hubbard bands and upper Hubbard bands. It was found that quasiparticle mass enhancement inferred by comparing γ to the density of states (DOS) at the Fermi level indicates the effective mass of CeSi₅ is enhanced with the fully relativistic results.     

Magnetic properties and 119Sn hyperfine interaction parameters of LiMn6Sn6

We have synthesized LiMn₆Sn₆, the first RMn₆Sn₆ compound involving an alkali metal as R element. It crystallizes in the hexagonal (P6/mmm) HfFe₆Ge₆-type structure. From magnetic measurements and powder neutron diffraction experiments it is found that LiMn₆Sn₆ magnetically orders at T_C = 380 K in a simple easy-plane ferromagnetic structure (m_Mn = 2.58 μ_B at 2 K). The ¹¹⁹Sn M?ssbauer spectrum recorded at 5 K indicates that the tin nuclei experience huge hyperfine fields (as large as 35 T). Electronic structure calculations are used to gain information about the microscopic origin of both the hyperfine field and electric field gradient at the Sn nuclei. The former arises due to spin-dependent hybridization between the 5s states of Sn and the 3d states of Mn. The latter comes from the 5p charge density close to the nucleus, whose anisotropy is mainly produced through directional interactions with the 3d states of the first Mn neighbors. Comparison between experimental quadrupole splittings and theoretical electric field gradients allows us to propose a value of for the quadrupole moment of the first excited state (I= 3/2) of the ¹¹⁹Sn nucleus.     

Electronic structure and magnetism of FeGe2

The electronic band structure of FeGe₂ has been calculated using the self-consistent full potential non-orthogonal local orbital minimum basis scheme based on the density functional theory. In the band structure of FeSn₂, Fe 3d and Sn 5p states play important roles near the Fermi level. Our calculations show that large enhancement of the static susceptibility over its non-interacting value is found due to a peak in the density of states at the Fermi level.     

Magnetic hyperfine structure of 119Sn in ferromagnetic Pd2MnSb

A magnetic hyperfine field of H = + 210 ± 5 kOe has been observed at Sn in Pd₂MnSb_0.99Sn_0.01 by Mössbauer spectroscopy on ¹¹⁹Sn. The significance of this measurement with respect to other hyperfine fields and theoretical calculations is discussed.