Influence of crystal structure,ligand environment and morphology on Co L‐edge XAS spectral characteristics in cobalt compounds

The electronic structure of a material plays an important role in its functionality for different applications which can be probed using synchrotron‐based spectroscopy techniques. Here, various cobalt‐based compounds, differing in crystal structure, ligands surrounding the central metal ion and morphology, have been studied by soft X‐ray absorption spectroscopy (XAS) at the Co L‐edge in order to measure the effect of these parameters on the electronic structure. A careful qualitative analysis of the spectral branching ratio and relative intensities of the L₃ and L₂ peaks provide useful insight into the electronic properties of compounds such as CoO/Co(OH)₂, CoCl₂.6H₂O/CoF₂.4H₂O, CoCl₂/CoF₂, Co₃O₄ (bulk/nano/micro). For further detailed analysis of the XAS spectra, quantitative analysis has been performed by fitting the spectral profile with simulated spectra for a number of cobalt compounds using crystal field atomic multiplet calculations.     

An unconventional method for measuring the Tc L3‐edge of technetium compounds

Tc L₃‐edge XANES spectra have been collected on powder samples of SrTcO₃ (octahedral Tc⁴⁺) and NH₄TcO₄ (tetrahedral Tc⁷⁺) immobilized in an epoxy resin. Features in the Tc L₃‐edge XANES spectra are compared with the pre‐edge feature of the Tc K‐edge as well as other 4d transition metal L₃‐edges. Evidence of crystal field splitting is obvious in the Tc L₃‐edge, which is sensitive to the coordination number and oxidation state of the Tc cation. The Tc L₃ absorption edge energy difference between SrTcO₃ (Tc⁴⁺) and NH₄TcO₄ (Tc⁷⁺) shows that the energy shift at the Tc L₃‐edge is an effective tool for studying changes in the oxidation states of technetium compounds. The Tc L₃‐edge spectra are compared with those obtained from Mo and Ru oxide standards with various oxidation states and coordination environments. Most importantly, fitting the Tc L₃‐edge to component peaks can provide direct evidence of crystal field splitting that cannot be obtained from the Tc K‐edge.     

The electron transport properties of pure liquid metals

Progress in the theory of the electrical conductivity and other ordinary transport properties of liquid metals since 1961 is reviewed. After a brief account of the basic nearly-free-electron diffraction formula, the quantitative comparison of this formula with experiment is discussed.

For the alkali metals, the agreement is adequate, given the uncertainty of the pseudopotentials, although there is controversy about the calculation of the temperature coefficient of ρ _L. To explain the observed volume dependence of ρ _L, and the thermoelectric power, it also seems necessary to allow for the variation of the pseudopotential with the positions of the Fermi level and the core levels relative to the bottom of the conduction band.

Quantitative results for the noble and polyvalent metals are meagre, and although calculations of ρ _L for Al and Zn are in excellent agreement with experiment there may be other cases where the basic formula is not adequate. The general question of the structure and convergence of the perturbation series for ρ _L is discussed, and it is suggested that corrections for higher order terms can be minimized by making the pseudopotential as near as possible to the t-matrix of an ion.

The anomalous properties of Hg are then discussed, in the light of the work of Mott (1966). In this connection it is shown that Edwards' formula (1962) for ρ _L, in which the Fermi velocity, v _F, is taken to be that of a free electron, ?k _F/m, despite deviations from the free-electron curve for ?(k), can be derived by using the expectation value of the current operator in place of e v _F in the Boltzmann equation. This modification of the elementary theory allows the Hall constant of a liquid metal to deviate from 1/nec, as found experimentally.     

Influence of natural aging on photoluminescence from porous silicon

The influence of natural aging on the photoluminescence intensity and the position of a photolu-minescence peak in n-type por-Si (por-Si) is studied. The variation of the phase composition and the relative content of the amorphous and oxide phases of silicon in por-Si during aging is determined by fitting simulated spectra to experimental ultrasoft Si L _2,3 X-ray emission spectra using reference spectra.     

Interaction of Short Laser Pulses in Wavelength Range from Infrared to X‐ray with Metals,Semiconductors, and Dielectrics

Laser‐matter interaction is defined by an electronic band structure of condensed matter and frequency ω_L of electromagnetic radiation. In the range of moderate fluences, the energy absorbed by electrons from radiation finally thermalizes in the ion thermal energy. The thermalization processes are different for optical as compared with X‐ray quanta and for metals relative to semiconductors and dielectrics, since the light absorption and electron‐electron, electron‐ion dynamics are sensitive to the electron population in a conduction band and the width of a forbidden gap. Although the thermalization processes are different, the final state is simply a heated matter. Laser heating creates powerful stresses in a target if duration of a laser pulse τ_L is short in acoustic time scale. Nucleation and material removal take place under such stresses. Such way of removal is called here the spallative ablation. Thus the spallative ablation is an ablation mechanism universally important for qualitatively different materials and quanta (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Intersubband transitions in Al0.82In0.18N/GaN single quantum well

The influence of the width of a lattice-matched Al_0.82In_0.18N/GaN single quantum well (SQW) on the absorption coefficients and wavelength of the intersubband transition (ISBT) has been investigated by solving the Schrödinger and Poisson equations self-consistently. The wavelength of 1—2 ISBT increases with L, the thickness of the single quantum well, ranging from 2.88 μm to 3.59 μm. The absorption coefficients of 1—2 ISBT increase with L at first and then decrease with L, with a maximum when L is equal to 2.6 nm. The wavelength of 1—3 ISBT decreases with L at first and then increases with L, with a minimum when L is equal to 4 nm, ranging from approximately 2.03 μm to near 2.11 μm. The absorption coefficients of 1—3 ISBT decrease with L. The results indicate that mid-infrared can be realized by the Al_0.82In_0.18N/GaN SQW. In addition, the wavelength and absorption coefficients of ISBT can be adjusted by changing the width of the SQW.     

X-ray magnetic circular dichroism sum rule correction for the light transition metals

Distinguishable L₂ and L₃ edges and a clear separation into j _3/2 and j _1/2 excitations are necessary for the application of L_2,3 edge X-ray magnetic circular dichroism (XMCD) sum rules, which provide element-specific information about spin and orbital magnetic moments. This separation is present for the heavy transition metals (TM), like Co and Ni, due to their large L_2,3 spin–orbit splitting. However, for the light TM, the 2p spin–orbit splitting is strongly reduced and quantum mechanical mixing of j _3/2 and j _1/2 excitations is present. This mixing reduces the observed XMCD related spin and magnetic dipole term contributions and prevents the direct application of XMCD spin sum rules. A large number of 2p?→?3d absorption spectra have been fitted nearly perfectly by a simple and phenomenological model, which takes into account lifetime effects and provides quantitative information about jj-mixing at the light TMs. On the basis of this mixing coefficient, sum rule correction factors have been determined. The proposed model results in renormalized magnetic projected XMCD spin moments, verified for different compounds of V, Cr, and Mn. A comparison with complementary methods gives consistent results. This or a similar fitting procedure and the estimated correction factors can be used in the future as a light element XMCD spin renormalization technique.     

Calculation of the ion transverse velocity distribution function under ion cyclotron resonance heating

The ion transverse velocity distribution functions and the fraction η of ions heated above a certain energy W ₁ are calculated as applied to the ion cyclotron resonance heating method of isotope separation. It is assumed that the longitudinal ion velocity distribution in a plasma source is nonequilibrium. Under high heating temperatures, the averaged ion transverse velocity distribution becomes essentially nonequilibrium and exhibits two maxima. The ion heating efficiency η is calculated for W ₁=40 eV and various values of the parameter p=λ/L, where λ is the wavelength of the electric field of an antenna and L is the heating zone extension. The relative contributions of the time-of-flight and Doppler broadenings are evaluated.     

Investigation of the multiplet features of SrTiO3 in X‐ray absorption spectra based on configuration interaction calculations

Synchrotron‐based L_2,3‐edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here, using the experimental Ti L_2,3‐edges absorption spectrum of SrTiO₃ as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L₃ and L₂ set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature are further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non‐linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO₃‐based thin films and heterostructures is offered. Detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the e_g crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.     

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.     

High speed all-silicon optical modulator

Electrorefractive effect is experimentally demonstrated in an all-silicon optical structure. A highly doped Si P⁺ layer is embedded in the intrinsic region of a PIN diode integrated in a SOI waveguide. Holes are confined at equilibrium around the P⁺ layer. By applying a reverse bias to the diode, electrical field sweeps the carriers out of the active region. Free carrier concentration variations are responsible for local refractive index variations leading to an effective index variation of the waveguide optical mode and to an optical absorption variation. As a figure of merit, the product V_πL_π, determined from the measured effective index variation, is equal to 3.1 V cm. Furthermore, the device performances have theoretically been investigated. Estimations show that V_πL_π as small as 1 V cm are feasible using optimized structures. Response times lower than 2 ps are predicted, which gives the possibility to achieve very high-speed modulation. Furthermore, a temperature increases from 300 to 400 K does not change the index variation amplitude, and despite the carrier mobility reduction, response times are still lower than 2 ps.     

Temperature dependence of the Ho L2‐edge XMCD spectra of Ho6Fe23

An X‐ray magnetic circular dichroism (XMCD) study performed at the Ho L_2,3‐edges in Ho₆Fe₂₃ as a function of temperature is presented. It is demonstrated that the anomalous temperature dependence of the Ho L₂‐edge XMCD signal is due to the magnetic contribution of Fe atoms. By contrast, the Ho L₃‐edge XMCD directly reflects the temperature dependence of the Ho magnetic moment. By combining the XMCD at both Ho L₂‐ and L₃‐edges, the possibility of determining the temperature dependence of the Fe magnetic moment is demonstrated. Then, both μ_Ho(T) and μ_Fe(T) have been determined by tuning only the absorption L‐edges of Ho. This result opens new possibilities of applying XMCD at these absorption edges to obtain quantitative element‐specific magnetic information that is not directly obtained by other experimental tools.     

Strong spin-dependent absorption at theL 2,-edges of 5d-impurities in iron

Large spin-dependent absorption effects have been observed with circularly polarized photons of energies between 10.8 keV and 13.8 keV at theL _2,3-edges of Os, Ir, Pt, and Au impurities (3 at.%) in iron. The largest value of the spin-dependent absorption coefficient (µ _c /µ _o +0.22) is found at the PtL ₂-edge. From the energy dependence of the spin-dependent absorption at theL ₂- andL ₃-edges the spin-density profiles of thed _3/2-andd _5/2-projected states populated in the absorption process are derived. Thed _5/2-spin densities deduced from theL ₃ spin-dependent absorption spectra agree well with spin-polarized band-structure calculations for the ferromagnetic ground state. A comparison of thed _3/2- andd _5/2-spin densities shows a strong contribution of the spin-orbit effects to the exchange splitting in Os, whereas only small spin-orbit effects are indicated for Ir, Pt and Au impurities.     

Effect of pressure on the Yb valency in YbS and YbTe

Abstract

We have measured L_III-edge x-ray absorption spectra (L_III-XA) of Yb in YbS and YbTe and optical reflectivity spectra of YbTe at pressures up to 34 GPa. In both materials the Yb ion undergoes a continuous valence change. In the case of YbS, the pressure-induced variation of the Yb mean valence v(I_III) agrees well with previous optical and lattice parameter studies. For YbTe, however, the XA data indicate the onset of a valence transition at a lower pressure (～10 GPa) than observed in optical spectra (～16 GPa). This behavior is explained by larger hybridization effects between the chalcogen p-bands and 4f states in YbTe as compared to YbS.     

Distribution and speciation of lead in model plant Arabidopsis thaliana by synchrotron radiation X‐ray fluorescence and absorption near edge structure spectrometry

To obtain reliable in situ information on the distribution and speciation of Pb in plants with low Pb content, special attention needs to be paid to the synchrotron radiation based micro‐X‐ray fluorescence and micro‐X‐ray absorption near edge structure (μ‐XANES) spectrometry to avoid specious results in the chosen XRF region of interest and speciation linear combination fitting. First, an Arabidopsis thaliana shoot cultured in a Pb solution is analyzed to obtain two‐dimensional Pb distribution graphs, where an overlap of Pb, As, Se, and Br lines in synchrotron radiation based micro‐X‐ray fluorescence spectra is found. To avoid this overlap, (1)As K‐L₃ and Pb L₃‐M₅, (2)As K‐M₃, (3)Pb L₂‐M₄, (4)Se K‐L₃, and (5)Br K‐M₃ lines should be chosen in the region of interest. The Pb content in the seed coat, root, and stem are 48.2, 17.3, and 5.8 times higher, respectively, than in the leaf, while the Pb content in the seed coat, root, stem, and leaf increased 3458, 1241, 420, and 72 times, respectively, compared with the A. thaliana sample without a Pb solution soak. Second, Pb speciation of the same shoot is analyzed using μ‐XANES. It is important to define a combination fitting range because different possible Pb combinations can emerge using different ranges. Different speciations were found in the root[Pb(Ac)₂ and PbSO₄], stem[Pb(Ac)₂ and Pb₃(PO₄)₂], leaf[Pb(OH)₂ and Pb₅Cl(PO₄)₃], and seed coat[Pb₃(PO₄)₂, Pb(OH)₂, and PbCO₃] between the fitting range of E₀ ? 20eV and E₀ + 70eV. A more complete Pb XANES database with more references, especially organic Pb compounds, is needed. Copyright © 2013 John Wiley & Sons, Ltd.     

苯甲酸-镝-钇配合物的发光

合成了苯甲酸-镝-钇固体配合物并研究了它们的光致发光性质.实验结果表明,当苯甲酸镝中部分Dy3+离子被Y3+离子取代时,可以便配合物中Dy3+离子的发光增强.     

Zur Theorie der kantenfernen Feinstruktur von Röntgenabsorptionsspektren

The extended fine structure of the X-ray absorption spectra of an atom in a chemical system depends on its orientation with respect to a polarized and nonpolarized X-ray beam. General equationes are developed to describe these dependences without consideration of spin-orbital interactions. Evidence is given for the validity of KOZLENKOV 's equation for the fine structure of polycrystalline solids, liquids, and gases. For the case of K absorption we obtain the equations formerly published by IZRAILEVA . Further, the explicite formulae for the L_III and L_III absorption fine structures are presented.     

Spin-dependent photoabsorption at theL-edges of ferromagnetic Gd and Tb metal

The spin-dependent absorption of circularly polarized x-rays is studied at theL-edges of ferromagnetic Gd and Tb metal. At theL ₁-edge a spin-dependent part of the absorption coefficient of 10^–3–10^–2 is observed. Strong resonance absorption known as white line occurs at theL ₂- andL ₃-absorption onset. Correlated with it one finds large spin-dependent absorption effects with amplitudes of a few percent. The spin-dependent absorption spectra reflect the profiles of the spin densities of the states populated in the absorption process. Thep-states show spin densities correlated with the first two flat bands above the Fermi level. The spin density of thed-like states is concentrated in the energy range of the white line. In Gd a splitting of (0.5–0.6) eV of the unoccupied 5d spin up and spin down bands is indicated for both spin-orbit partners. In Tb a large dependence of the 5d spin density on the spin-orbit configuration is observed. The experimental results on the spin densities in Gd are compared with band structure calculations for the ferromagnetic ground-state. The theoretical and experimental spin density profiles agree well for thep-states but not for thed-states. The discrepancy concerning thed-states may be attributed to core-hole polarization effects in the absorption process.     

pH-dependent kinetics of MgCl2 adsorption under a fatty-acid Langmuir film

The effect of subphase pH (5.5 and 10.5) on the structure of behenic-acid monolayers was investigated during Mg²⁺ adsorption by means of Grazing Incidence X-ray Diffraction (GIXD) and Brewster Angle Microscopy (BAM). The final phase corresponding to an ion superlattice commensurate to the behenic-acid cell is pH-independent. In contrast, the sequence of phases evidenced from the initial L₂-phase to this final state presents at pH 10.5 an additional stage associated to a film condensation toward the L' ₂-phase. The structures of the intermediate states preceding the superstructure nucleation are slightly different, both with a short-range fatty-acid order. Finally, a laser light effect that could result from visible light absorption by the inorganic complexes is evidenced in the final state as well as in the intermediate phases.     

Vortex rings and plasma toroidal vortices in a homogeneous infinite medium. I. Maximum vortex path

The maximum path L _MAX of vortex rings (toroidal vortices) in air and water before the beginning of their decay was experimentally determined in a wide variation range of their initial integral characteristics. A formula for L _MAX was derived as a function of primary characteristics of such vortices from the laws of their motion and energy variation. It was shown that this formula is in satisfactory agreement with experimental data.