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.     

Soft X-ray magnetic circular dichroism of Heusler-type alloy Co2MnGe

Co and Mn 2p core absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectra have been measured for the ferromagnetic ternary alloy Co₂MnGe. The observed Co 2p XAS spectrum can be understood on the basis of the unoccupied Co 3d partial density of states, whereas the overall features of the Mn 2p XAS and XMCD spectra have been partly reproduced by the Mn 2p⁵3d⁶ final state multiplets. We have found that the orbital polarization of the Co 3d and even the Mn 3d states are recognizable, which suggests that a spin-orbit coupling should be taken into account in the energy band structure in order to reproduce the half metallic nature of this alloy.     

Electronic structure of CeAl2 thin films studied by X-ray absorption spectroscopy

We report X-ray absorption near edge structures (XANES) study of CeAl₂ thin films of various thicknesses, 40-120 nm, at Al K- and Ce L₃-edges. The threshold of the absorption features at the Al K-edge shifts to the higher photon energy side as film thickness decreases, implying a decreased in Al p-orbital charges. On the other hand, from Ce L₃-edge spectra, we observed a decrease in the 5d4f occupancy as the surface-to-bulk ratio increases. The valence of Ce in these thin films, as revealed by the Ce L₃-edge spectral results, is mainly trivalent. From a more detailed analysis we found a small amount of Ce⁴⁺ contribution, which increases with decreasing film thickness. Our results indicate that the surface-to-bulk ratio is the key factor which affects the electronic structure of CeAl₂ thin films. The above observations also suggest that charge transfer from Al to Ce is associated with the decrease of the film thickness.     

X-ray magnetic circular dichroism at rare-earth L23 absorption edges in various compounds and alloys

Theoretical interpretations of X-ray magnetic circular dichroism (XMCD) at rare-earth (called R hereafter) L₂₃ absorption edges are reviewed using differing models, depending on the material under investigation. In the first chapter, we present an overview of recent developments for XMCD in XAS with a few general remarks, especially at R atom absorption edges. In Section 2, we first describe basic mechanism of XMCD at L₂₃ edges of R systems, and then we essentially discuss two examples of XMCD spectra in: (i) R₂Fe₁₄B metallic compounds, with the help of a cluster model, and (ii) RFe₂ Laves-phase compounds, using a tight-binding approximation for R 5d and Fe 3d conducting states. A good agreement between theory and experiment for R₂Fe₁₄B suggests that a cluster model provides a valuable method to quantitatively calculate XMCD spectra of R systems, even with quite complicated atomic arrangements. For RFe₂ systems the XMCD spectral shape, especially for the L₂ edge of heavy R elements, is more complicated than those of R₂Fe₁₄B systems, and this is explained by the competition of some different XMCD mechanisms. In Section 3, we focus on special series of Ce systems, related to XAS and XMCD studies at the Ce L₂₃ edges. Two clearly differing cases are interpreted: (i) A well localized 4f¹ system, i.e. CeRu₂Ge₂; (ii) A less localized 4f¹ system, i.e. CeFe₂, with a 3d partner. Then, from a more experimental point of view, we investigate the influence of substitution on the low temperature properties of CePd₃ compounds, i.e. Ce(_Pd1-xMnx)3$\mathrm{Ce}({\mathrm{Pd}}_{1-x}{\mathrm{Mn}}_x{)}_3$ alloys where x   is about 0.03, giving rise to (_CePd3)8Mn$({\mathrm{CePd}}_3{)}_8\mathrm{Mn}$ ordered structure. We give another example: Ce(_Pd1-xNix)3$\mathrm{Ce}({\mathrm{Pd}}_{1-x}{\mathrm{Ni}}_x{)}_3$ alloys with x taken up to about 0.25. Also the Ce L₂₃ XMCD signal measured in pure CePd₃ demonstrates that in the Ce based dense Kondo materials, only the 4f¹ channel yields a magnetic response.     

Neuropsychological constraints to human data production on a global scale

High-magnetic-field X-ray absorption spectra (XAS) and its X-ray magnetic circular dichroism (XMCD) at the Yb L_2, 3 edges of YbInCu₄ are calculated around the field-induced valence transition at about 30 T. The calculations are made by using a new theoretical framework with an extended single impurity Anderson model (SIAM) developed recently by the present author. Two parameters in SIAM, the 4f level and the hybridization strength, are taken as different values in low- and high-magnetic-field phases of the field-induced valence transition. The calculated results are compared with recent experimental data measured by Matsuda et al. by utilizing a miniature pulsed magnet up to 40 T. The field-dependence of the calculated XMCD spectra is explained in detail on the basis of the field-dependence of the Yb 4f wavefunctions in the ground state. Some possibilities are discussed on the negative XMCD signal observed experimentally at the L₂ edge.     

Electronic structure and magnetic properties of the compound CeCuIn

Magnetization, magnetic susceptibility, electrical resistivity, thermoelectric power and X-ray photoemission measurements were performed on a polycrystalline sample of CeCuIn. This compound crystallizes in a hexagonal structure of the ZrNiAl type. The magnetic data indicate that CeCuIn remains paramagnetic down to 1.9 K with a paramagnetic Curie temperature of −13 K and an effective magnetic moment equal to 2.5 μ_B. The electrical resistivity has metallic character, yet in the entire temperature range studied here, it is a strongly nonlinear function of temperature. The temperature dependence of the thermoelectric power is dominated by a small positive maximum near 76 K and a deep negative minimum at about 16 K. Above 150 K the thermopower exhibits a Mott's type behavior. The positive sign of the Seebeck coefficient in this temperature region indicates that the holes are dominant charge and heat carriers. The structure of Ce 3d_5/2 and Ce 3d_3/2 XPS spectra has been interpreted in terms of the Gunnarsson-Schönhammer theory. Three final-state contributions f⁰, f¹ and f² are clearly observed, which exhibit a spin-orbit splitting Δ_SO≈18.7 eV. The appearance of the 3d⁹f⁰ component is a clear evidence of the intermediate valence behavior of Ce. From the intensity ratio I(f⁰)/[I(f⁰)+I(f¹)+I(f²)] the 4f-occupation number is estimated to be 0.95. In turn, the ratio I(f²)/[I(f¹)+I(f²)]=0.08 yields a measure of the hybridization energy that is equal to 45 meV.     

ESR of Gd-impurities in the heavy fermion compounds CeCu2Si2 and CeAl3

The heavy fermion systems CeCu₂Si₂ and CeAl₃ are characterized by a huge quasiparticle density of states responsible for the large electronic specific heat. The observation of a Gd³⁺ electron spin resonance (ESR) in single crystals CeCu₂Si₂ and in polycrystalline CeAl₃ clearly demonstrates the local character of these quasiparticles. Nevertheless, the Gd-spin relaxation shows remarkable anomalies with respect to the isostructural compounds LaCu₂Si₂ and LaAl₃: Probably via RKKY coupling, Ce 4f-spin fluctuations give rise to an enhanced Gd-spin relaxation resulting in an unusual non-linear thermal broadening around the Kondo temperature. From this we obtain information about the temperature dependence of the Ce 4f-spin correlation time.     

Resonant inelastic X-ray scattering and its magnetic circular dichroism

Magnetic circular dichroism in resonant inelastic X-ray scattering (MCD-RIXS) of ferromagnetic systems is discussed for the longitudinal geometry (LG), where the directions of incident X-ray and magnetization are parallel, and the transverse geometry (TG), where they are perpendicular. MCD-RIXS in LG is represented by two successive real processes, X-ray absorption and X-ray emission, while MCD-RIXS in TG is given by the interference process. We describe an application of MCD-RIXS in LG to the detection of Ce 4f² contribution in Ce, L₃ absorption edge of CeFe₂, and theoretical and experimental studies of MCD-RIXS in TG for Gd and Sm systems.     

Electronic and Magnetic States of Pr and Mn in the Pr<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> Films Studied by XANES and XMCD Spectroscopy

The spectral dependences of X-ray absorption near-edge spectroscopy (XANES) and X-ray magnetic circular dichroism (XMCD) and the field dependences of XMCD near the K edge of Mn and the L_2,3 edges of Pr in the Pr_0.8Sr_0.2MnO₃ and Pr_0.6Sr_0.4MnO₃ films at T = 90 K are studied. The spectral dependences point to a mixed valence state of Mn and Pr in the films. It is found that, as compared to XANES, XMCD is more sensitive to the valence state of Pr⁴⁺. The field dependences of XMCD point to ferromagnetic behavior of Mn ions and the Van Vleck paramagnetism of Pr ions, which makes a significant contribution to the total magnetization of the films. It is shown that as the Sr concentration increases, the XMCD intensity at the K edge of Mn increases, which indicates a growth of the total magnetic moment of the film due to an increase in the 4p–3d hybridization.     

Low-temperature properties of the Ce(Pd1−xNix) system

The influence of substituting Pd by Ni is described in Ce(Pd_1-xNi_x)₃ alloys with x taken up to about 0.25. Thermal and magnetization measurements point out a transition from a non-magnetic state (CePd₃) to a ferromagnetic state for x > 0.05, with a Curie temperature K. The Ce-L_2,3 absorption edges and magnetic circular dichroism (XMCD) study reveals the coexistence of strong 4f hybridization and ferromagnetic order. The Ce-L_2,3 XMCD signal measured in CePd₃ demonstrates that in the Ce-based dense Kondo materials only the 4f¹ channel gives a magnetic response.Received: 2 September 2003, Published online: 15 March 2004PACS: 75.20.Hr Local moment in compounds and alloys; Kondo effect, valence fluctuations, heavy fermions - 75.30.Mb Valence fluctuation, Kondo lattice, and heavy-fermion phenomena - 71.10.Hf Non-Fermi-liquid ground states, electron phase diagrams and phase transitions in model systems     

Crystal and electronic structure and magnetic properties of CeRhPb

The new intermetallic cerium compound CeRhPb was synthesized by arc melting and studied by means of X-ray diffraction and magnetic measurements. The crystal structure determined from the single-crystal X-ray data is of the ZrNiAl type (space group P6¯2m). The compound was found to be a Pauli paramagnet with 4f⁰ ground state of the Ce atoms. The ab-initio band structure calculations performed without and with spin polarization confirmed the nonmagnetic character of the plumbide studied.     

Identification of local magnetic contributions in a Co2FeBO5 single crystal by XMCD spectroscopy

The temperature dependences of the X-ray absorption spectra (XAS) and of the spectra of X-ray magnetic circular dichroism (XMCD) are measured near the L _3,2 absorption edges of Co and Fe in ludwigite Co₂FeBO₅ single crystals. The antiparallel orientation of the magnetic moments of cobalt and iron is demonstrated. The coercive fields related to cobalt and iron ions are determined. The orbital (m _l ) and (m _s ) spin contributions to the total magnetic moments of cobalt and iron ions are identified. The ratios and relative directions of m _l and m _s are found.     

27Al pulsed nuclear magnetic resonance study of CeAl2

The magnetic properties and the electronic structures of a rare-earth aluminum intermetallic compound CeAl₂ are investigated by magnetic susceptibility measurements and ²⁷Al pulsed nuclear magnetic resonance (NMR) techniques. The magnetic susceptibility is strongly temperature-dependent, following a Curie–Weiss law down to ∼12 K, and shows an antiferromagnetic transition at 4 K. The ²⁷Al NMR spectra show a typical powder pattern for a nuclear spin I of 5/2 with the second-order nuclear quadrupole interaction at high temperature and an additional large dipolar broadening between the 4f electron spins of cerium and the ²⁷Al nuclear spins at low temperature. The ²⁷Al NMR Knight shift follows the same temperature dependence as the magnetic susceptibility, suggesting that the ²⁷Al NMR Knight shift originates from the transferred hyperfine field of the Ce 4f electron spins with the hyperfine coupling constant of A = +5.7 kOe/μ_B. The spin-lattice relaxation rate 1/T₁ is roughly proportional to temperature, as with most non-magnetic metals at high temperature, and then strongly temperature-dependent, increasing rapidly with a peak near the antiferromagnetic transition temperature and decreasing at lower temperature. The temperature dependence of the Korringa ratio K, however, suggests that the antiferromagnetic spin fluctuation signature, which is an enhancement in the Korringa ratio, is washed out owing to the geometrical cancellation of Ce 4f fluctuations at the Al sites.     

Magnetic properties of deposited gadolinium atoms,dimers and their monoxides

Magnetic properties of gadolinium clusters deposited on magnetic ultrathin Fe/Cu(100) films have been measured using X-ray Magnetic Circular Dichroism spectroscopy (XMCD). 3d↦4f as well as 4d↦4f absorption spectra are presented and discussed. Changes in the relative peak intensities between the monomer, dimer and the corresponding monoxides are observed for the multiplets. The comparison with bulk measurements and calculations exhibit a transition from atomic like to bulk like properties.     

Localization for 4f electrons in a heavy fermion compound CeCu2Si2: Insights from dynamical mean-field theory

A first principles calculation is carried out on a typical heavy fermion system-CeCu₂Si₂ by using a many-body method combing density functional theory (DFT) and dynamical mean-field theory (DMFT) along with the on-site Coulomb repulsion (represented by the Hubbard U parameter) for capturing the electronic correlation due to the incompletely filled Ce 4f orbitals. The results establish that the average occupation of Ce 4f electrons n_f is about 1.02 (mainly 4f¹ atomic configuration), close to the nominal occupation in pure Ce metal and in good agreement with the spectrum function in this work and the available experimental observations. The imaginary part of the impurity Green function indicates that the Ce 4f j = 5/2 and j = 7/2 states have metallic and insulating behavior, respectively. The dehybridization between the Ce 4f orbitals and ligand valence orbitals in the vicinity of the Fermi level is responsible for the localized 4f state and heavy fermionic behavior in this system.     

Characterization of different magnetite–cobalt nanoparticles in hydrocarbon-based magnetic fluids by means of static and dynamic magnetization measurements

Magnetic nanoparticles with different compositions (Co_xFe_3−xO₄, 0?x?0.1) were synthesized from metal salts using a coprecipitation technique to produce magnetic fluids following a peptization technique. The liquid carrier was the hydrocarbon Isopar M and the surfactant was oleic acid. The colloidal-sized ferrimagnetic nanoparticles produced were found to be superparamagnetic. Measurements of the complex magnetic susceptibility were carried out to evaluate the resonant frequency f_res, the anisotropy constant K, and anisotropy field H_A. f_res was found to be a linear function of the cobalt content of the magnetic nanoparticles over the range of cobalt content studied.     

Crystal field effect on X-ray magnetic circular dichroism spectra at the L<Subscript>2,3</Subscript> absorption edges of mixed-valence Ce and Yb compounds in high magnetic fields

A theoretical study is presented, with an extended single impurity Anderson model, for the crystal field effect on the X-ray magnetic circular dichroism (XMCD) spectra at L_2,3 edges of mixed-valence Ce and Yb compounds in high magnetic fields. The crystal field acting on the 4f electrons is assumed to have cubic symmetry. Due to the competition among the effects of crystal field, mixed valency, and external magnetic field, the magnetic-field-dependence of XMCD spectra exhibits a variety of features; for instance, the branching ratio, R(L₂/L₃), of L₂ and L₃ XMCD intensities of Ce compounds can take R(L₂/L₃) > 1.0 and <1.0, and that of Yb compounds can take R(L₂/L₃) > 0 and <0. It is shown that the magnetic-field-dependence of the total XMCD intensity I(L₂ + L₃) is proportional to the magnetization curve, but that of R(L₂/L₃) gives more precise information on the ground state wavefunction in magnetic fields. A new and useful method to correlate the XMCD spectra, the 4f magnetization and the ground state wavefunction is proposed and used to discuss the relation between I(L₂ + L₃) and the magnetization curve and that between R(L₂/L₃) and the ground state wavefunction.     

Resistance minimum of the Kondo-type in non-dilute magnetic systems

Using Nagaoka's decoupled equations of motion for double-time Green's functions an approximate integral equation is derived and solved numerically for the self-energy of conduction electrons in intermetallic compounds containing a non-dilute and translationally symmetric system of magnetic rare-earth ions. These latter are assumed to interact with an antiferromagnetics-f exchange parameter with the conduction electrons. The resistivity is computed and compared with experimental values for CeAl₂ and CeAl₃.     

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.     

Thermal phase transition of RbMnFe(CN)6 observed by X-ray emission and absorption spectroscopy

The thermal phase transition of RbMnFe(CN)₆ has been observed by Mn and Fe 3p-1s X-ray emission spectroscopy (XES) and 1s X-ray absorption spectroscopy (XAS). The thermal variations of the spin states and the valences of Mn and Fe were determined to be Mn²⁺(S=5/2)-NC-Fe³⁺(S=1/2) for the high-temperature (HT) phase and Mn³⁺(S=2)-NC-Fe²⁺(S=0) for the low-temperature (LT) phase. These transitions are thus caused by charge transfer between Mn and Fe. The temperature dependences of Mn and Fe 3p-1s XES and 1s XAS were observed as the composition of the spectra of the HT and LT phases. The ratios of the HT component in each spectrum show good agreement with the thermal transition curves observed with magnetic susceptibility measurements.