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Two isomeric ruthenium(II)/5,10,15,20-tetraphe-nylporphyrin complexes featuring axially coordinated redox-active, low-optical gap 2- or 6-isocyanoazulene ligands have been isolated and characterized by NMR, UV-vis, and magnetic circular dichroism (MCD) spectroscopic methods, high-resolution mass spectrometry, and single-crystal X-ray crystallography. The UV-vis and MCD spectra support the presence of the low-energy, azulene-centered transitions in the Q band region of the porphyrin chromophore. The first coordination sphere in new L2RuTPP complexes reflects compressed tetragonal geometry. The redox properties of the new compounds were assessed by electrochemical and spectroelectrochemical means and correlated with the electronic structures predicted by density functional theory and CASSCF calculations. Both experimental and theoretical data are consistent with the first two reduction processes involving the axial azulenic ligands, whereas the oxidation profile (in the direction of increasing potential) is exerted by the ruthenium ion, the porphyrin core, and the axial azulenic moieties.

While x-ray absorption spectroscopy is mainly governed by electric-dipole transitions, the technique of nonresonant inelastic x-ray scattering (NIXS) offers the possibility to explore higher-order multipole transitions. These transitions obey different selection rules that can reach final states of higher angular momenta, opening complementary spectroscopic perspectives. Here, we investigate the suitability of NIXS to study transuranium compounds. We show that the $K$ edge of the Be encapsulation can be practically fully excluded by using the imaging capabilities of the technique arising from the position of the signals on the multidetector. Experimental results for the multipole transitions at the actinide ${O}_{4,5}$ edges (90--120 eV) in ${\mathrm{UO}}_{2}$, ${\mathrm{NpO}}_{2}$, ${\mathrm{PuO}}_{2}$, and ${\mathrm{Pu}}_{2}{\mathrm{O}}_{3}$ are compared with multielectronic calculations. The spectral features are shown to be very sensitive to the ratio of the triakontadipole and octupole transitions, which could potentially be used to assess the radial expansion of the $5f$ wave function, which is expected to occur in covalent mixing with the O $2p$ states.

Rare-earth-based (RE) nanolaminates have attracted attention recently because of their complicated magnetism and their potential as precursors for strongly correlated two-dimensional materials. In this work, we synthesized a class of nanolaminates with a Mo4RE4Al7C3 chemistry, where RE = Ce or Pr. Powder samples of both phases were characterized with respect to structure and composition. Single crystals of Mo4Ce4Al7C3 were used for magnetization measurements. The crystal structure was investigated by means of x-ray diffraction and scanning transmission electron microscopy. Magnetization analysis reveals a ferromagnetic ground state with a Curie temperature of similar to 10.5 K. X-ray absorption near-edge structure provides experimental evidence that Ce is in a mixed-valence state. X-ray magnetic circular dichroism shows that only the Ce atoms with 4f(1) configuration occupying one of the two possible sites are ferromagnetically coupled, with a saturation moment of similar to 1.2 mu(B) per atom. We thus classify Mo4Ce4Al7C3 as a ferromagnetic, mixed-valence compound. Funding Agencies|Knut and Alice Wallenberg (KAW) Foundation through a Fellowship [0358, KAW 2015.0043]; Swedish Research council [642-2013-8020]; Flag-ERA JTC; chair of excellence program of the Nanosciences Foundation (Universite Grenoble-Alpes Foundation); Federation Wallonie-Bruxelles through the Action de Recherche Concertee "3D nanoarchitecturing of 2D crystals" [16/21-077]; European Union [696656]; Belgium FNRS (Flag-ERA) [R. 50.01.18.F]; Fonds de la Recherche Scientifique de Belgique (F.R.S. -FNRS) [2.5020.11]; Linkoping Ultra Electron Microscopy Laboratory

First-order magnetic transitions (FOMTs) with a large discontinuity in magnetization are highly sought in the development of advanced functional magnetic materials. Isosymmetric magnetoelastic FOMTs that do not perturb crystal symmetry are especially rare, and only a handful of material families, almost exclusively transition metal-based, are known to exhibit them. Yet, here we report a surprising isosymmetric FOMT in a rare-earth intermetallic, Eu2In. What makes this transition in Eu2In even more remarkable is that it is associated with a large latent heat and an exceptionally high magnetocaloric effect in low magnetic fields, but with tiny lattice discontinuities and negligible hysteresis. An active role of the Eu-5d and In-4p states and a rather unique electronic structure borne by In to Eu charge transfer, altogether result in an unusual exchange mechanism that both sets the transition in motion and unveils an approach toward developing specific magnetic functionalities ad libitum., First order magnetic phase transitions have many practical applications but they often involve structural changes that make it difficult to control energy losses. Guillou et al. show that Eu2In has an isostructural transition with a mechanism distinct from other known magnetoelastic transitions.

Magneto-optical response, i.e. optical response in the presence of a magnetic field, is commonly used for characterization of materials and in optical communications. However, quantum mechanical description of electric and magnetic fields in crystals is not straightforward as the position operator is ill defined. We present a reformulation of the density matrix perturbation theory for time-dependent electromagnetic fields under periodic boundary conditions, which allows us to treat the orbital magneto-optical response of solids at the \textit{ab initio} level. The efficiency of the computational scheme proposed is comparable to standard linear-response calculations of absorption spectra and the results of tests for molecules and solids agree with the available experimental data. A clear signature of the valley Zeeman effect is revealed in the continuum magneto-optical spectrum of a single layer of hexagonal boron nitride. The present formalism opens the path towards the study of magneto-optical effects in strongly driven low-dimensional systems., Comment: 12 pages, 3 figures

Dihydroxyacid dehydratase (DHAD) is the third enzyme required for branched-chain amino acid biosynthesis in bacteria, fungi, and plants. DHAD enzymes contain two distinct types of active-site Fe–S clusters. The best characterized examples are Escherichia coli DHAD, which contains an oxygen-labile [Fe(4)S(4)] cluster, and spinach DHAD, which contains an oxygen-resistant [Fe(2)S(2)] cluster. Although the Fe–S cluster is crucial for DHAD function, little is known about the cluster-coordination environment or the mechanism of catalysis and cluster biogenesis. Here, using the combination of UV-visible absorption and circular dichroism and resonance Raman and electron paramagnetic resonance, we spectroscopically characterized the Fe–S center in DHAD from Arabidopsis thaliana (At). Our results indicated that AtDHAD can accommodate [Fe(2)S(2)] and [Fe(4)S(4)] clusters. However, only the [Fe(2)S(2)] cluster–bound form is catalytically active. We found that the [Fe(2)S(2)] cluster is coordinated by at least one non-cysteinyl ligand, which can be replaced by the thiol group(s) of dithiothreitol. In vitro cluster transfer and reconstitution reactions revealed that [Fe(2)S(2)] cluster–containing NFU2 protein is likely the physiological cluster donor for in vivo maturation of AtDHAD. In summary, AtDHAD binds either one [Fe(4)S(4)] or one [Fe(2)S(2)] cluster, with only the latter being catalytically competent and capable of substrate and product binding, and NFU2 appears to be the physiological [Fe(2)S(2)] cluster donor for DHAD maturation. This work represents the first in vitro characterization of recombinant AtDHAD, providing new insights into the properties, biogenesis, and catalytic role of the active-site Fe–S center in a plant DHAD.

Metal-exchanged zeolites are a class of heterogeneous catalysts that perform important functions ranging from selective hydrocarbon oxidation to remediation of NO x pollutants. Among these, copper and iron zeolites are remarkably reactive, hydroxylating methane and benzene selectively at low temperature to form methanol and phenol, respectively. In these systems, reactivity occurs at well-defined molecular transition metal active sites, and in this review we discuss recent advances in the spectroscopic characterization of these active sites and their reactive intermediates. Site-selective spectroscopy continues to play a key role, making it possible to focus on active sites that exist within a distribution of inactive spectator metal centers. The definition of the geometric and electronic structures of metallozeolites has advanced to the level of bioinorganic chemistry, enabling direct comparison of metallozeolite active sites to functionally analogous Fe and Cu sites in biology. We identify significant parallels and differences in the strategies used by each to achieve high reactivity, highlighting potentially interesting mechanisms to tune the performance of synthetic catalysts. ispartof: Chemical Reviews vol:118 issue:5 pages:2718-2768 ispartof: location:United States status: published

In this review we provide an overview of the potential of synchrotron radiation techniques to understand the structural and electronic properties of coordination compounds. Besides the largely employed multi-wavelength anomalous dispersion (MAD) and X-ray absorption spectroscopy (XAS), in both near (XANES) and post (EXAFS) edge regions, we also discuss the contribution arising from more specialized techniques that have become more widely used in the last years, such as the total scattering approach in the XRPD data analysis and X-ray emission spectroscopy (XES). Comparison with the commonly used laboratory techniques (XRD, UV–vis, luminescence, NMR, EPR) is used to underline the added value of synchrotron radiation techniques when applied to already well characterized samples. The fundamental role of DFT calculations in interpreting both diffraction and spectroscopic data to understand structural and electronic properties of coordination complexes is highlighted. A perspective summary is reported at the end of the manuscript.

Ferrites with (inverse) spinel structure display a large variety of electronic and magnetic properties, making some of them interesting for potential applications in spintronics. We investigate the thermally induced interdiffusion of Ni2+ ions out of NiO into Fe3O4 ultrathin films, resulting in off-stoichiometric nickel ferrite-like thin layers. We synthesized epitaxial Fe3O4/NiO bilayers on Nb-doped SrTiO3(001) substrates by means of reactive molecular beam epitaxy. Subsequently, we performed an annealing cycle comprising three steps at temperatures of 400 degrees C, 600 degrees C, and 800 degrees C under an oxygen background atmosphere. We studied the changes of the chemical and electronic properties as result of each annealing step with help of hard x-ray photoelectron spectroscopy and found a rather homogeneous distribution of Ni and Fe cations throughout the entire film after the overall annealing cycle. For one sample we observed a cationic distribution close to that of the spinel ferrite NiFe2O4. Further evidence comes from low-energy electron diffraction patterns indicating a spinel-type structure at the surface after annealing. Site-and element-specific hysteresis loops performed by x-ray magnetic circular dichroism uncovered the antiferrimagnetic alignment between the octahedral coordinated Ni2+ and Fe3+ ions and the Fe3+ ion in tetrahedral coordination. We find a quite low coercive field of 0.02 T, indicating a rather low defect concentration within the thin ferrite films.

We report on the synthesis, crystal structure and magnetic characterisation of the trinuclear, fluoride-bridged, molecular nanomagnet [Dy(hfac)(3)(H2O)-CrF2(py)(4)-Dy(hfac)(3)(NO3)] (1) (hfacH = 1,1,1,5,5,5-hexafluoroacetylacetone, py = pyridine) and a closely related dinuclear species [Dy(hfac)(4)-CrF2( py)(4)]center dot 1/2 CHCl3 (2). Element-specific magnetisation curves obtained on 1 by X-ray magnetic circular dichroism (XMCD) allow us to directly observe the field-induced transition from a ferrimagnetic to a ferromagnetic arrangement of the Dy and Cr magnetic moments. By fitting a spin-Hamiltonian model to the XMCD data we extract a weak antiferromagnetic exchange coupling of j -0.18 cm(-1) between the Dy-III and Cr-III ions. The value found from XMCD is consistent with SQUID magnetometry and inelastic neutron scattering measurements. Furthermore, alternating current susceptibility and muon-spin relaxation measurements reveal that 1 shows thermally activated relaxation of magnetisation with a small effective barrier for magnetisation reversal of Delta(eff) 3 cm(-1). Density-functional theory calculations show that the Dy-Cr couplings originate from superexchange via the fluoride bridges.

Ferrites with (inverse) spinel structure display a large variety of electronic and magnetic properties making some of them interesting for potential applications in spintronics. We investigate the thermally induced interdiffusion of Ni$^{2+}$ ions out of NiO into Fe$_3$O$_4$ ultrathin films resulting in off-stoichiometric nickelferrite-like thin layers. We synthesized epitaxial Fe$_3$O$_4$/NiO bilayers on Nb-doped SrTiO$_3$(001) substrates by means of reactive molecular beam epitaxy. Subsequently, we performed an annealing cycle comprising three steps at temperatures of 400\,$^{\circ}$C, 600\,$^{\circ}$C, and 800\,$^{\circ}$C under an oxygen background atmosphere. We studied the changes of the chemical and electronic properties as result of each annealing step with help of hard x-ray photoelectron spectroscopy and found a rather homogenous distribution of Ni and Fe cations throughout the entire film after the overall annealing cycle. For one sample we observed a cationic distribution close to that of the spinel ferrite NiFe$_2$O$_4$. Further evidence comes from low energy electron diffraction patterns indicating a spinel type structure at the surface after annealing. Site and element specific hysteresis loops performed by x-ray magnetic circular dichroism uncovered the antiferrimagnetic alignment between the octahedral coordinated Ni$^{2+}$ and Fe$^{3+}$ ions and the Fe$^{3+}$ in tetrahedral coordination. We find a quite low coercive field of 0.02\,T, indicating a rather low defect concentration within the thin ferrite films., Comment: 9 pages, 8 figures

The previous Reviews in Mineralogy volume on spectroscopic methods (Vol. 18 Spectroscopic Methods in Mineralogy and Geology, Frank C. Hawthorne, ed. 1988), contained a single chapter on X-ray absorption spectroscopy which reviewed aspects of both EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near-Edge Structure) (Brown et al. 1988, Chapter 11) However, since publication of that review there have been considerable advances in our understanding of XANES theory and applications. Hence EXAFS and XANES have been separated into their own individual chapters in the current volume. In this chapter we endeavor to bring the reader up to date with regard to current XANES theories, as well as, introducing them to the common applications of the technique in mineralogy, geochemistry and materials science. There have been several reviews of XANES (cf., Brown et al. 1988, Brown and Parks 1989, Manceau et al. 2002, Brown and Sturchio 2002, Mottana 2004, Rehr and Ankudinov 2005, de Groot 2001, 2005, and papers therein). In this chapter on XANES it is not our intention to provide a comprehensive review of all the XANES studies since 1988 but to summarize what X-ray edges are commonly investigated and what one can expect to be able to extract from the data. The reader is also advised to read the chapters in this volume on analytical transmission electron microscopy by Brydson et al. (2014, this volume) where (core level) electron energy loss (EELS) spectroscopy is discussed, and by Lee et al. (2014, this volume) on X-ray Raman spectroscopy (XRS), as these techniques provide element specific information similar to XANES. X-ray absorption near-edge structure (XANES) spectroscopy using synchrotron radiation is a well-established technique providing information on the electronic, structural and magnetic properties of matter. In XANES, a photon is absorbed and an electron is excited from a core state to an empty state. To excite an electron in a given core-level, the photon energy has to be equal or higher than the binding energy of this core-level. This gives rise to the opening of a new absorption channel when the photon energy is scanned. The energy of an absorption edge therefore corresponds to the core-level energy, which is characteristic for each element, making XANES an element-selective technique. In addition to the XANES region, at higher energies the extended X-ray absorption fine structure (EXAFS) region is found. The spectral shape in the near-edge region is determined by electronic density of states effects and gives mainly information about the electronic properties and the local geometry of the absorbing atom. The EXAFS region is dominated by single scattering events of the outgoing electron on the neighboring atoms, providing mainly information about the local geometric structure around the absorbing site. In this chapter we will focus on XANES.

We have observed a large exchange bias field H-E approximate to 2460 Oe and a large coercive field H-C approximate to 6200 Oe at T = 2 K for Co/CoO core-shell nanoparticles (similar to 4 nm diameter Co metal core and CoO shell with similar to 1 nm thickness) embedded in a non-magnetic MgO matrix. Our results are in sharp contrast to the small exchange bias and coercive field in the case of a non-magnetic Al2O3 or C matrix materials reported in previous studies. Using soft X-ray magnetic circular dichroism at the Co-L-2,L-3 edge, we have observed a ferromagnetic signal originating from the antiferromagnetic CoO shell. This gives direct evidence for the existence of rotatable interfacial uncompensated Co spins in the nominally antiferromagnetic CoO shell, thus supporting the uncompensated spin model as a microscopic description of the exchange bias mechanism.

International audience; Ribonucleotide reductase (RNR) catalyzes the rate limiting step in DNA synthesis where ribonucleotides are reduced to their corresponding deoxyribonucleotides. They are formed through a radical-induced reduction of ribonucleotides. Three classes of RNR generate the catalytically active site thiyl radical using different co-factors: a tyrosyl-radical in most cases (class I), homolytic cleavage of deoxyadenosyl-cobalamin (class II), or a glycyl-radical (class III), respectively. Class I RNR has a larger subunit R1/R1E containing the active site and a smaller subunit R2/R2F with (the thiyl-generating power from) a tyrosyl radical or an oxidized iron-manganese cluster and is reviewed herein. Class I is divided into subclasses, Ia (tyrosyl-radical and di-iron-oxygen cluster), Ib (tyrosyl-radical and di-manganese-oxygen cluster) and Ic (an iron-manganese cluster). Presented here is an overview of recent developments in the understanding of class I RNR: metal-ion cluster identities, novel 3D structures, magnetic-optical properties, and reaction mechanisms. It became clear in the last years that the primitive bacterial RNR sources can utilize different metal-ion clusters to fulfil function. Within class Ia that includes members from eukaryotes (mammalians, fish) and some viruses species, the presence of hydrogen bonding interactions from water at different distances with the tyrosyl-radical site can occur. This demonstrates a large versatility in the mechanism to form the thiyl radical.

Fluorescence yield (FY) detected x-ray absorption spectra (XAS) of 3d transition metal ions are calculated from the integrated 2p3d resonant x-ray emission spectra. The resulting FY-XAS spectra are compared with the normal XAS spectra corresponding to the absorption cross section and significant deviations between the two spectra are found. This implies that the assumption that the FY-XAS spectrum identifies with the XAS spectrum is disproved. Especially for the early transition metal systems the differences between the FY-XAS and XAS are large, due to the opening of inelastic decay channels from selected x-ray absorption final states. The theoretical calculations show that the difference between FY detection and XAS is largest for the detection in depolarized geometry. The calculations are compared with experimental spectra for oxides and coordination compounds for Fe2+, Co2+ and Ni2+ systems. The implications for the sum rules in XAS and magnetic circular dichroism experiments are discussed.

In this work we present measurements of the switching of the Faraday effect in metal-organic compounds. Faraday rotation is the rotation of the plane of polarization of linearly polarized light under the influence of a magnetic field in the direction of propagation of the light. It is the magnetic equivalent of circular birefringence and is related to magnetic circular dichroism via the Kramers-Kronig transformation. The Faraday effect is used in optical isolators and magnetic sensors. Faraday rotation and magnetic circular dichroism spectra have been calculated and measured for various nanoparticles, nanocomposites, magnetic fluids and metal-organic complexes. These measurements and calculations indicate that it is possible to change the magneto-optical response by changing the state of the molecule, such as a change in protonation or oxidation state. The molecular environment also influences the magneto-optical spectra of metal-organic complexes and organic molecules. Thus it is possible to change the Faraday rotation spectrum by modifying the molecular environment or the molecule itself. We have measured the reversible switching of the magneto-optical response by these principles. This easily induced reversible switching opens the possibility of new devices such as switchable optical isolators.

Fluorescence yield (FY) detected x-ray absorption spectra (XAS) of 3d transition metal ions are calculated from the integrated 2p3d resonant x-ray emission spectra. The resulting FY-XAS spectra are compared with the normal XAS spectra corresponding to the absorption cross section and significant deviations between the two spectra are found. This implies that the assumption that the FY-XAS spectrum identifies with the XAS spectrum is disproved. Especially for the early transition metal systems the differences between the FY-XAS and XAS are large, due to the opening of inelastic decay channels from selected x-ray absorption final states. The theoretical calculations show that the difference between FY detection and XAS is largest for the detection in depolarized geometry. The calculations are compared with experimental spectra for oxides and coordination compounds for Fe2+, Co2+ and Ni2+ systems. The implications for the sum rules in XAS and magnetic circular dichroism experiments are discussed.

11 pages, 6 figures, 1 table, 1 appendix., We describe a setup for the x-ray detection of ferromagnetic resonance in the longitudinal geometry using element-specific transmission measurements. Thin magnetic film samples are placed in a static magnetic field collinear with the propagation direction of a polarized soft x-ray beam and driven to ferromagnetic resonance by a continuous wave microwave magnetic field perpendicular to it. The transmitted photon flux is measured both as a function of the x-ray photon energy and as a function of the applied static magnetic field. We report experiments performed on a 15 nm film of doped Permalloy (Ni73Fe18Gd7Co2) at the L3/L2-edges of Fe, Co, and Ni. The achieved ferromagnetic resonance sensitivity is about 0.1 monolayers/ (raiz cuadrada de Hz). The obtained results are interpreted in the framework of a conductivity tensor based formalism. The factors limiting the sensitivity as well as different approaches for the x-ray detection of ferromagnetic resonance are discussed., Financial support from the European Research Council (Starting Grant No. 203239 ) and the Spanish Ministerio de Ciencia e Innovación (Grant No. HA2007-0098) is gratefully acknowledged.

We present a line-shape analysis based on atomic single configuration Mn 3d6 multiplet calculations of core-level and valence-band spectroscopy data from metallic ferromagnetic Mn5Ge3. We show that atomic calculations can fit most of the spectral features measured in Mn 2p-3d x-ray absorption and circular dichroism, in Mn 2p and Mn 3s core-level photoemission, as well as for the delocalized electrons in valence-band photoemission. This indicates that, in spite of the metallic nature of the compound, atomic effects can play a relevant role to determine the physical properties of the Mn5Ge3 system.

Molecular {Cr7Ni} rings have shown several ideal features for the observation of quantum phenomena and they appear suitable candidates for qubits encoding at low temperatures. We have exploited different functionalization pathways to graft molecular {Cr7Ni} rings onto a Au(111) surface from the liquid phase and here we report a comparative analysis of the results obtained by STM, XPS, XAS and XMCD experimental techniques.

We predict very strong peak enhancements in core-level photoemission at the resonance with a deeper core-level absorption. This allows a straightforward interpretation of core-level spectroscopy in two ways: (a) photoemission peaks can be resolved in resonance with different x-ray absorption peaks, and (b) x-ray absorption peaks can be resolved using partial electron yield at constant binding energy. This can be used to study covalency effects in transition-metal, rare-earth, and actinide compounds. An example is given for nickel metal using a cluster calculation including multiplet structure.

We discuss the electronic state of Ni atoms in Ni metal and of Ni impurity in Cu and Au metals from the viewpoint of 3d configuration interaction (CI) using the Anderson impurity model including atomic multiplets. On the basis of the discussion, we give an interpretation for the Ni 2p-core X-ray photoemission spectrum (2p XPS) in Ni metal and Ni impurity systems and 3d photoemission spectra in Ni metal. The interpretation is, furthermore, shown to be consistent with the previous one for the 2p --> 3d circularly polarized X-ray absorption in ferromagnetic Ni using the CI approach.

We show that double-resonance spectra recorded during the simultaneous absorption of x-ray and microwave (MW) photons are a fingerprint of the perturbed electronic configuration of atomic species driven to ferromagnetic resonance. X-ray absorption measurements performed as a function of x-ray energy and polarization over the Fe L2,3 edges of single-crystal yttrium-iron garnet reveal MW-induced multiplet features related to angular momentum transfer from the MW field to localized Fe 3d magnetic sublevels. O K-edge absorption spectra demonstrate the formation of dynamic 2p-orbital magnetization components at O sites coupled to the Fe magnetic moments at tetrahedral and octahedral sites. These results are compared with double-resonance x-ray absorption spectra of Permalloy, showing that the MW transition probability is distributed according to the hybridization character of the 3d states and proportional to the unperturbed unoccupied magnetic density of states of metals and insulators.

In this study, we provide evidence of surface ferromagnetism in a thin metallic Mn:Ge(111) layer displaying a (root 3 x root 3)R30 degrees reconstruction. Magnetic circular dichroism effects are observed in remanence below the Curie temperature in both x-ray absorption spectroscopy and valence-band photoemission spectra, the latter indicating that spin-polarized states are present within 2 eV below the Fermi edge.

We report on a study of $M$ edges of transition metals and their oxides performed by using high-order harmonics of ultrafast laser pulses and synchrotron radiation. Data of the Mn, Fe, and Co $3p$ edges demonstrate that laser harmonics in the extreme ultraviolet range are suited for spectroscopy of solids. These results open perspectives for measurements which could in the future be performed in time-resolved mode. Resonant reflectivity of Fe, Co, ${\mathrm{Fe}}_{2}{\mathrm{O}}_{3}$, and $\mathrm{CoO}$ measured at the synchrotron complements the experiment by providing the detailed line shape of the refraction index for reference.

The x-ray photoemission spectrum of the valence states of 3d transition-metal systems is spin polarized when using circularly polarized photons. The integral of the spin-orbit spectrum is proportional to the expectation value of the angular part of the 3d spin-orbit operator in the initial state. We show that this quantity can be used to get an estimate of the atomic orbital moment. While the measurement is sensitive to the magnetization axis, it does not require a net macroscopic magnetization nor the presence of a long-range magnetic order, and is therefore suitable for any transition-metal systems being antiferromagnetic or paramagnetic or magnetically disordered. In the case of full 3d shell the integral of the spin-orbit spectrum is zero, but the spectral shape can give a direct estimate of the 3d spin-orbit energy splitting DeltaE(SO). We have used Cu and CoO to experimentally test this technique. As expected Cu provides a vanishing result for , whereas for Co2+ in CoO we find =1.36h at 0 K. On the other hand we find DeltaE(SO)similar or equal to280 meV for Cu.

We review the basic electronic structure of cuprate systems, and discuss the importance of strong electron correlation effects. Using resonant photoelectron spectroscopy it is demonstrated that the undoped cuprates belong to the class of charge-transfer insulators. As a consequence, the first ionization states are likely to consist of bound states with a compensated local spin structure rather than the usual high spin states expected from Hund’s first rule. Using spin-resolved resonant photoemission with circularly-polarized light, we are able to unravel the different spin states of the valence band spectrum of the undoped cuprates and show that the top of the band is of pure singlet character, which provides strong support for the existence and stability of Zhang–Rice singlets in high- T C superconductors.

0038-1101; The Tb3+ absorption line F-7(6)-->D-5(4) Of the Terbium Gallium Garnet crystal is excited with an Argon ion laser. The Verdet's constant has been determined and reported against 1/lambda(2), showing no significant resonant behaviour at absorption resonance. The utility and the constraints of the crystal at this particular resonant wavelength are pointed out. (C) 1998 Elsevier Science Ltd. All rights reserved.

We predict very strong peak enhancements in core-level photoemission at the resonance with a deeper core-level absorption. This allows a straightforward interpretation of core-level spectroscopy in two ways: (a) photoemission peaks can be resolved in resonance with different x-ray absorption peaks, and (b) x-ray absorption peaks can be resolved using partial electron yield at constant binding energy. This can be used to study covalency effects in transition-metal, rare-earth, and actinide compounds. An example is given for nickel metal using a cluster calculation including multiplet structure.

We discuss the electronic state of Ni atoms in Ni metal and of Ni impurity in Cu and Au metals from the viewpoint of 3d configuration interaction (CI) using the Anderson impurity model including atomic multiplets. On the basis of the discussion, we give an interpretation for the Ni 2p-core X-ray photoemission spectrum (2p XPS) in Ni metal and Ni impurity systems and 3d photoemission spectra in Ni metal. The interpretation is, furthermore, shown to be consistent with the previous one for the 2p --> 3d circularly polarized X-ray absorption in ferromagnetic Ni using the CI approach.