M5 Edge Research Articles

Europium Cyclooctatetraene Nanowire Carpets: A Low-Dimensional, Organometallic, and Ferromagnetic Insulator.

We investigate the magnetic and electronic properties of europium cyclooctatetraene (EuCot) nanowires by means of low-temperature X-ray magnetic circular dichroism (XMCD) and scanning tunneling microscopy (STM) and spectroscopy (STS). The EuCot nanowires are prepared in situ on a graphene surface. STS measurements identify EuCot as an insulator with a minority band gap of 2.3 eV. By means of Eu M5,4 edge XMCD, orbital and spin magnetic moments of (-0.1 ± 0.3)μB and (+7.0 ± 0.6)μB, respectively, were determined. Field-dependent measurements of the XMCD signal at the Eu M5 edge show hysteresis for grazing X-ray incidence at 5 K, thus confirming EuCot as a ferromagnetic material. Our density functional theory calculations reproduce the experimentally observed minority band gap. Modeling the experimental results theoretically, we find that the effective interatomic exchange interaction between Eu atoms is on the order of millielectronvolts, that magnetocrystalline anisotropy energy is roughly half as big, and that dipolar energy is approximately ten times lower.

Circular dichroism and angular deviation in x-ray absorption spectra of Dy2ScN@C80 single-molecule magnets on h−BN/Rh(111)

Endohedral fullerenes, such as Dy2ScN@C80, are single-molecule magnets with long relaxation times of their magnetization. An open and anisotropic 4f electron shell in the lanthanides (here Dy) imposes a magnetic moment that maintains its orientation at liquid-helium temperatures for macroscopic times. If these molecules shall be used as single-bit information storage elements or for quantum operations, the orientation of the endohedral units and the orientation of the magnetic moments has to be controlled. X-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD)—with variation of the angle of x-ray incidence—allows for the detection of these two structural elements. We present XMCD data of Dy2ScN@C80 on an h−BN/Rh(111) nanomesh that display at 2 K a large hysteresis with a coercive field of 0.4 T. The angular dependence of the XAS data at the Dy M5 edge indicates partial ordering of the endohedral units. In order to quantify anisotropic orientation we introduce the “deviation” D as an operational quantity that measures differences between two spectra.

Towards the surface hydroxyl species in CeO2 nanoparticles.

Understanding the complex chemistry of functional nanomaterials is of fundamental importance. Controlled synthesis and characterization at the atomic level is essential to gain deeper insight into the unique chemical reactivity exhibited by many nanomaterials. Cerium oxide nanoparticles have many industrial and commercial applications, resulting from very strong catalytic, pro- and anti-oxidant activity. However, the identity of the active species and the chemical mechanisms imparted by nanoceria remain elusive, impeding the further development of new applications. Here, we explore the behavior of cerium oxide nanoparticles of different sizes at different temperatures and trace the electronic structure changes by state-of-the-art soft and hard X-ray experiments combined with computational methods. We confirm the absence of the Ce(iii) oxidation state at the surface of CeO2 nanoparticles, even for particles as small as 2 nm. Synchrotron X-ray absorption experiments at Ce L3 and M5 edges, combined with X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and small angle X-ray scattering (SAXS) and theoretical calculations demonstrate that in addition to the nanoceria charge stability, the formation of hydroxyl groups at the surface profoundly affects the chemical performance of these nanomaterials.

Differential uranyl(v) oxo-group bonding between the uranium and metal cations from groups 1, 2, 4, and 12; a high energy resolution X-ray absorption, computational, and synthetic study.

The uranyl(vi) 'Pacman' complex [(UO2)(py)(H2L)] A (L = polypyrrolic Schiff-base macrocycle) is reduced by Cp2Ti(η2-Me3SiC[triple bond, length as m-dash]CSiMe3) and [Cp2TiCl]2 to oxo-titanated uranyl(v) complexes [(py)(Cp2TiIIIOUO)(py)(H2L)] 1 and [(ClCp2TiIVOUO)(py)(H2L)] 2. Combination of ZrII and ZrIV synthons with A yields the first ZrIV-uranyl(v) complex, [(ClCp2ZrOUO)(py)(H2L)] 3. Similarly, combinations of Ae0 and AeII synthons (Ae = alkaline earth) afford the mono-oxo metalated uranyl(v) complexes [(py)2(ClMgOUO)(py)(H2L)] 4, [(py)2(thf)2(ICaOUO)(py) (H2L)] 5; the zinc complexes [(py)2(XZnOUO)(py)(H2L)] (X = Cl 6, I 7) are formed in a similar manner. In contrast, the direct reactions of Rb or Cs metal with A generate the first mono-rubidiated and mono-caesiated uranyl(v) complexes; monomeric [(py)3(RbOUO)(py)(H2L)] 8 and hexameric [(MOUO)(py)(H2L)]6 (M = Rb 8b or Cs 9). In these uranyl(v) complexes, the pyrrole N-H atoms show strengthened hydrogen-bonding interactions with the endo-oxos, classified computationally as moderate-strength hydrogen bonds. Computational DFT MO (density functional theory molecular orbital) and EDA (energy decomposition analysis), uranium M4 edge HR-XANES (High Energy Resolution X-ray Absorption Near Edge Structure) and 3d4f RIXS (Resonant Inelastic X-ray Scattering) have been used (the latter two for the first time for uranyl(v) in 7 (ZnI)) to compare the covalent character in the UV-O and O-M bonds and show the 5f orbitals in uranyl(vi) complex A are unexpectedly more delocalised than in the uranyl(v) 7 (ZnI) complex. The Oexo-Zn bonds have a larger covalent contribution compared to the Mg-Oexo/Ca-Oexo bonds, and more covalency is found in the U-Oexo bond in 7 (ZnI), in agreement with the calculations.

Theoretical Modelling of High-Resolution X-Ray Absorption Spectra at Uranium M4 Edge

ABSTRACTWe investigate the origin of satellite features that appear in the high-resolution x-ray absorption spectra measured at the uranium M4 edge in compounds where the uranium atoms are in the U6+ oxidation state. We employ a material-specific Anderson impurity model derived from the electronic structure obtained by the density-functional theory.

Trends in the valence band electronic structures of mixed uranium oxides.

The valence band electronic structures of mixed uranium oxides (UO2, U4O9, U3O7, U3O8, and β-UO3) have been studied using the resonant inelastic X-ray scattering (RIXS) technique at the U M5 edge and computational methods. We show here that the RIXS technique and recorded U 5f-O 2p charge transfer excitations can be used to test the validity of theoretical approximations.

Interplay of Fe and Tm moments through the spin-reorientation transition in TmFeO3

X-ray magnetic circular and linear dichroism (XMCD and XMLD) have been used to investigate the Fe magnetic response during the spin reorientation transition (SRT) in TmFeO3. These experiments are complemented with resonant magnetic diffraction experiments at the Tm M5 edge to study simultaneously the induced magnetic order in the Tm 4f shell and the behavior of the Tm orbitals through the SRT. Comparing the Fe XMLD results with neutron diffraction and magnetization measurements on the same sample indicate that the SRT has an enhanced temperature range in the near surface region. This view is supported by the resonant soft x-ray diffraction results at the Tm M5 edge. These find an induced magnetic moment on the Tm sites, which is well-described by a dipolar mean field model originating from the Fe moments. Even though such a model can describe the 4f response in the experiments, it is insufficient to describe the SRT even when considering a change in the 4f anisotropy. Moreover, the results of the Fe XMCD are indicative of a decoupling of spin canting and antiferromagnetic spin rotation in the near surface regime close to the SRT, which remains to be understood.

Pu Coexists in Three Oxidation States in a Borosilicate Glass: Implications for Pu Solubility.

Pu(III), Pu(IV), and a higher oxidation state of Pu, likely Pu(VI), are for the first time characterized simultaneously present in a borosilicate glass using Pu M5 edge high energy resolution X-ray absorption near edge structure (HR-XANES) technique. We illustrate that the method can be very efficiently used to determine Pu oxidation states, which control the solubility limit of Pu in a glass matrix. HR-XANES results show that the addition of excess Si3N4 is not sufficient for complete reduction of Pu to Pu(III), which has a relatively high solubility limit (9-22 wt % Pu) due to its network-modifying behavior in glasses. We provide evidence that the initially added Pu(VI) might be partly preserved during vitrification at 1200/1400 °C in Ar atmosphere. Pu(VI) could be very advantageous for vitrification of Pu-rich wastes, since it might reach solubility limits of 40 wt % comparable to U(VI).

Evolution of the Uranium Chemical State in Mixed-Valence Oxides.

A fundamental question concerning the chemical state of uranium in the binary oxides UO2, U4O9, U3O7, U3O8, and UO3 is addressed. By utilizing high energy resolution fluorescence detection X-ray absorption near edge spectroscopy (HERFD-XANES) at the uranium M4 edge, a novel technique in the tender X-ray region, we obtain the distribution of formal oxidation states in the mixed-valence oxides U4O9, U3O7, and U3O8. Moreover, we clearly identify a pivot from U(IV)-U(V) to U(V)-U(VI) charge compensation, corresponding with transition from a fluorite-type structure (U3O7) to a layered structure (U3O8). Such physicochemical properties are of interest to a broad audience of researchers and engineers active in domains ranging from fundamental physics to nuclear industry and environmental science.

Prominent role of oxygen in the multiferroicity ofDyMnO3andTbMnO3: A resonant soft x-ray scattering spectroscopy study

Oxygen is known to play an important role in the multiferroicity of rare earth manganites; however, how this role changes with rare earth elements is still not fully understood. To address this question, we have used resonant soft x-ray scattering spectroscopy to study the F-type (0,τ,0) diffraction peak from the antiferromagnetic order in DyMnO3 and TbMnO3. We focus on the measurements at O K edge of these two manganites, supplemented by the results at Mn L2 and Dy M5 edge of DyMnO3. We show that the electronic states of different elements are coupled more strongly in DyMnO3 than in TbMnO3, presumably due to the stronger lattice distortion and the tendency to develop E-type antiferromagnetism in the ferroelectric state that promote the orbital hybridization. We also show that the anomaly in the correlation length of (0,τ,0) peak in DyMnO3 signifies the exchange interaction between Mn and rare earth spins. Our findings reveal the prominent role of oxygen orbitals in the multiferroicity of rare earth manganites and the distinct energetics between them.

Probing Covalency in the UO3 Polymorphs by U M4 edge HR- XANES

Local atomic and electronic structure investigations of uranium trioxide (UO3) crystalline phases performed by the U M4 edge HR-XANES technique is presented. The experimental U M4 edge HR-XANES spectra of α-UO3, β-UO3 and γ-UO3 polymorphic phases are compared with spectra of uranate (CaU2O7) and uranyl (UO3•1-2(H2O)) compounds. We describe a finger print approach valuable for characterization of variations of U-O axial bond lengths. Theoretical calculations of spectra using full-multiple-scattering theory (FEFF9.6 code) are performed. We have tested and selected input parameters, which provide best agreement between experimental and calculated spectra.

Aqueous U(VI) interaction with magnetite nanoparticles in a mixed flow reactor system: HR-XANES study

The redox variations and changes in local atomic environment of uranium (U) interacted with the magnetite nanoparticles were studied in a proof of principle experiment by the U L3 and M4 edges high energy resolution X-ray absorption near edge structure (HR-XANES) technique. We designed and applied a mixed flow reactor (MFR) set-up to maintain dynamic flow conditions during U-magnetite interactions. Formation of hydrolyzed, bi- and poly-nuclear U species were excluded by slow continuous injection of U(VI) (10-6 M) and pH control integrated in the MFR set-up. The applied U HR-XANES technique is more sensitive to minor changes in the U redox states and bonding compared to the conventional XANES method. Major U(VI) contribution in uranyl type of bonding is found in the magnetite nanoparticles after three days operation time of the MFR. Indications for shortening of the U-Oaxial bond length for the magnetite compared to the maghemite system are present too.

Quadrupole moments in chiral materialDyFe3(BO3)4observed by resonant x-ray diffraction

By means of circularly polarized x-ray beam at Dy L3 and Fe K absorption edges, the chiral structure of the electric quadrupole was investigated for a single crystal of DyFe3(BO3)4 in which both Dy and Fe ions are arranged in spiral manners. The integrated intensity of the resonant x- ray diffraction of space-group forbidden reflections 004 and 005 is interpreted within the electric dipole transitions from Dy 2p3 to 5d and Fe 1s to 4p, respectively. We have confirmed that the 2 handedness of the crystal observed at Dy L3 and Fe K edges is consistent with that observed at Dy M5 edge in the previous study. By analyzing the azimuth scans of the diffracted intensity, the electronic quadrupole moments of Dy 5d and Fe 4p are derived. The temperature profiles of the integrated intensity of 004 at the Dy L3 and the Fe K edges are similar to those of Dy-O and Fe-O bond lengths, while that at the Dy M5 edge does not. The results indicate that the helix chiral orientations of quadrupole moments due to Dy 5d and Fe 4p electrons are more strongly affected by the crystal fields than Dy 4f.

Optical constants of e-beam-deposited zirconium dioxide measured in the 55-150 Å wavelength region using the reflectivity technique.

In the present study, optical constants of e-beam-deposited zirconium dioxide (ZrO2) thin film are determined in the 55-150 Å soft x-ray wavelength region using the angle-dependent reflectivity technique. Soft x-ray reflectivity measurements are carried out using the reflectivity beamline at the Indus-1 synchrotron radiation source. Derived optical constants (δ and β) are compared with the tabulated values of Henke et al. [http://henke.lbl.gov/optical_constants/asf.html]. It is found that the measured δ values are consistently lower than the tabulated bulk values in the 70-150 Å wavelength region. In this region, the delta values are lower by 19%-24% from the tabulated data. Below the Zr M4 edge (66.3 Å), a deviation in delta values is found as ∼2%-21%. These changes are attributed to growth-related defects (oxygen and voids) and variation in film stoichiometry. To the best of our knowledge, the present study gives the first reported experimental values of optical constants for ZrO2 in the 55-150 Å wavelength region.

Optical properties of zirconium carbide in 60-200 Å wavelength region using x-ray reflectivity technique.

Optical constants of zirconium carbide (ZrC) have been determined in the soft x-ray region of 60-200 Å wavelength using angle-dependent x-ray reflectivity measurements. Reflectivity measurements are carried out at the reflectivity beamline of the Indus-1 synchrotron radiation source. Derived optical constants (δ and β) are compared with the tabulated values [At. Data Nucl. Data Tables 54, 181 (1993)]. The optical constants are 15%-35% lower than bulk values in the 60-200 Å wavelength region. Near the Zr M4 edge 187 eV (66.3 Å), the δ values were close to bulk values with a deviation of 5%-10%. A large deviation of ∼20% was found in beta values especially near the Zr M4 edge region, whereas it was in close agreement in the wavelength range away from the edge. To the best of our knowledge, this paper gives the first reported experimental values of optical constants for zirconium carbide in the 60-200 Å wavelength region.

X-ray induced demagnetization of single-molecule magnets

Low-temperature x-ray magnetic circular dichroism measurements on the endohedral single-molecule magnet DySc2N@C80 at the Dy M4,5 edges reveal a shrinking of the opening of the observed hysteresis with increasing x-ray flux. Time-dependent measurements show that the exposure of the molecules to x-rays resonant with the Dy M5 edge accelerates the relaxation of magnetization more than off-resonant x-rays. The results cannot be explained by a homogeneous temperature rise due to x-ray absorption. Moreover, the observed large demagnetization cross sections indicate that the resonant absorption of one x-ray photon induces the demagnetization of many molecules.

M sub-shell X-ray fluorescence cross-section measurements in high Z elements with X-ray tube photon source

X-ray tube has been used for selective M sub-shell excitations in a single reflection set-up for Pt, Au, Pb, Th and U required for M sub-shell fluorescence cross-sections measurements. Weighted photon energy and total intensity of the incident flux between E M5 edge and tube anode voltage were evaluated following a specific procedure. Comparison of measured cross-sections with the calculated ones from existing DHS/DF model based theoretical data on atomic parameters lend support to the present findings.

Coherent magnetic diffraction from the uranium M4 edge in the multi-k magnet, USb

The slow magnetic dynamics, from seconds to kiloseconds, of the canonical 3-k antiferromagnet USb have been probed, using X-ray photon correlation spectroscopy (XPCS). In this work, XPCS is combined with resonant X-ray diffraction to focus on scattering at an antiferromagnetic Bragg peak. High quality coherent magnetic diffraction patterns were recorded (speckle contrast of ~ 88%) and magnetic domains were observed; the number of domains increases on warming to T* ~ 160 K, where the spin waves soften to zero frequency, and again on warming to TN = 218 K. The intensity auto-correlation, g2(t), is primarily static over 1000 s, with a small dynamical process (change of ~ 0.4%) that increases in rate close to the transitions.

The europium oxidation state in CsSrI3:Eu scintillators measured by X-ray absorption spectroscopy

Divalent Eu is a common luminescence activator in inorganic scintillators due to its allowed 5d–4f transitions. Since Eu can exist in both divalent and trivalent states, but only luminescence from divalent Eu is suitable for scintillation applications, it is important to determine the potential presence of trivalent Eu in the crystal. We report measurements of Eu(II) and Eu(III) in the new CsSrI3:Eu scintillator using X-ray absorption spectroscopy. Single crystals of CsSr0.93Eu0.07I3 were grown from the melt via the Bridgman method using EuI2 powder as a source of divalent Eu activators. The X-ray absorption spectra on the Eu M4 and M5 edges were obtained at beamline 4.0.2 at the Advanced Light Source synchrotron. The results were compared to model samples of trivalent and divalent europium, which provided clear signatures of the two oxidation states. The measured electronic structure of Eu confirms predominant Eu(II) in both the EuI2 starting material and the CsSr0.93Eu0.07I3 scintillator crystals. However, a small presence of Eu(III) points to the partial oxidation of europium, especially at the sample surface.

Role of critical spin fluctuations in ultrafast demagnetization of transition-metal rare-earth alloys

Ultrafast magnetization dynamics induced by femtosecond laser pulses have been measured in ferrimagnetic Co0.8Gd0.2, Co.74Tb.26 and Co.86Tb.14 alloys. Using element sensitivity of X-ray magnetic circular dichroism at the Co L3, Tb M5 and Gd M5 edges we evidence that the demagnetization dynamics is element dependent. We show that a thermalization time as fast as 280 fs is observed for the rare-earth in the alloy, when the laser excited state temperature is below the compensation temperature. It is limited to 500 fs when the laser excited state temperature is below the Curie temperature (Tc). We propose critical spin fluctuations in the vicinity of TC as the mechanism which reduces the demagnetization rates of the 4f electrons in transition-metal rare-earth alloys whereas at any different temperature the limited demagnetization rates could be avoided.