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Thole, B. T.; Laan, G. van der; Fuggle, J. C.; Sawatzky, G. A.; Karnatak, R.C.; Esteva, J.M.

doi:10.1103/physrevb.32.5107

Cited by 735 publications

(509 citation statements)

References 37 publications

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“…XAS and XMCD data of samples AÀC measured at the Er M 4,5 edge are shown in Figure 3. The absorption spectra exhibit the characteristic triple-peak structure corresponding to the ΔJ = 0, ( 1 transitions from the filled 3d to the open 4f shell of the Er III ion 40 indicating that the Er ion retains its 4 I 15/2 ground state also in close proximity to the metal surfaces. Ligand-field effects are virtually not seen in the M 4,5 XAS because of the dominating spinÀorbit coupling and electronÀelectron interaction.…”

Section: Resultsmentioning

confidence: 99%

Exchange Interaction of Strongly Anisotropic Tripodal Erbium Single-Ion Magnets with Metallic Surfaces

et al. 2014

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We present a comprehensive study of Er(trensal) single-ion magnets deposited in ultrahigh vacuum onto metallic surfaces. X-ray photoelectron spectroscopy reveals that the molecular structure is preserved after sublimation, and that the molecules are physisorbed on Au(111) while they are chemisorbed on a Ni thin film on Cu(100) single-crystalline surfaces. X-ray magnetic circular dichroism (XMCD) measurements performed on Au(111) samples covered with molecular monolayers held at temperatures down to 4 K suggest that the easy axes of the strongly anisotropic molecules are randomly oriented. Furthermore XMCD indicates a weak antiferromagnetic exchange coupling between the single-ion magnets and the ferromagnetic Ni/Cu(100) substrate. For the latter case, spin-Hamiltonian fits to the XMCD M(H) suggest a significant structural distortion of the molecules. Scanning tunneling microscopy reveals that the molecules are mobile on Au(111) at room temperature, whereas they are more strongly attached on Ni/Cu(100). X-ray photoelectron spectroscopy results provide evidence for the chemical bonding between Er(trensal) molecules and the Ni substrate. Density functional theory calculations support these findings and, in addition, reveal the most stable adsorption configuration on Ni/Cu(100) as well as the Ni–Er exchange path. Our study suggests that the magnetic moment of Er(trensal) can be stabilized via suppression of quantum tunneling of magnetization by exchange coupling to the Ni surface atoms. Moreover, it opens up pathways toward optical addressing of surface-deposited single-ion magnets.

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Section: Resultsmentioning

confidence: 99%

Exchange Interaction of Strongly Anisotropic Tripodal Erbium Single-Ion Magnets with Metallic Surfaces

et al. 2014

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“…Quantitative information about bonding, back-bonding, charge-transfer and spin character could be obtained by modelling the XA spectra using charge-transfer multiplet theory, 17,20,24 which has proven its validity in interpreting transition metal L-edge spectra in systems such as molecules, condensed matter and proteins. Briefly, the theory begins with the Hamiltonian of the metal atom, taking into account all Coulomb interactions, as well as spin-orbit coupling between the atomic orbitals.…”

Section: Charge-transfer Multiplet Calculationsmentioning

confidence: 99%

Retracted Article: On the enzymatic activity of catalase: an iron L-edge X-ray absorption study of the active centre

Bergmann

Bonhommeau

Lange

et al. 2010

Phys. Chem. Chem. Phys.

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Catalase and methaemoglobin have very similar haem groups, which are both ferric, yet catalase decomposes hydrogen peroxide to water and oxygen very efficiently, while methaemoglobin does not. Structural studies have attributed this behaviour to their different distal environments. Here we present Fe L 2,3 -edge X-ray absorption spectra of these proteins in physiological solutions, which reveal clear differences in their electronic structures, in that p back-donation of the Fe atom occurs in catalase, which confers on it a partial ferryl (Fe 4+ ) character, while this is not the case in methaemoglobin. The origin of the Fe 4+ character stems from the proximal tyrosine residue. We also find that both systems are in a high spin state. Temperature effects influence the spectra of catalase only weakly, in agreement with previous studies of its chemical activity. We conclude that the high activity of catalase is not only determined by its distal environment but also by its partial ferryl character.

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“…Cerium can be found in the +4 formal oxidation state in some non-molecular, extended solids such as Cs2CeCl6 and other binary halides, [3][4][5][6] CeO2, 7 Ce(SO4)2, 8 and [NH4]2[Ce(NO3)6], 9-10 among others. 11 These materials have been the subject of numerous synchrotron radiation based spectroscopy experiments, including X-ray photoelectron spectroscopy, 12 resonant inelastic X-ray scattering, 13 and X-ray absorption spectroscopies at the cerium L3, [7][8][14][15][16][17][18][19][20][21][22] M5,4-, 12,19,[23][24][25][26][27][28][29][30] and N5,4-edges, 12 as well as ligand K-edges. [31][32] Some of these studies have presented evidence for the importance of both 4f and 5d orbital contributions to covalency in Ce bonding.…”

Section: Introductionmentioning

confidence: 99%

A Macrocyclic Chelator That Selectively Binds Ln⁴⁺ over Ln³⁺ by a Factor of 10²⁹

et al. 2016

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Abstract.A tetravalent cerium macrocyclic complex (CeLK4) was prepared with an octadentate terephthalamide ligand comprised of hard catecholate donors, and characterized in the solution state by spectrophotometric titrations and electrochemistry, and in the crystal by X-ray diffraction. The solution state studies showed that L exhibits a remarkably high affinity towards Ce 4+ , with log β110 = 61(2) and ΔG = -348 kJ/mol, compared with log β110 = 32.02(2) for the analogous Pr 3+ complex. In addition, L exhibits an unusual preference for forming CeL 4-relative to formation of the analogous actinide complex, ThL 4-, which has β110 = 53.7(5). The extreme stabilization of tetravalent cerium relative to its trivalent state is also evidenced by the shift of 1.91 V in redox potential of the Ce 3+ /Ce 4+ couple of the complex (measured at -0.454 V vs. SHE). The unprecedented behavior prompted an electronic structure analysis using L3 and M5,4-edge X-ray absorption near-edge structure (XANES) spectroscopies and configuration interaction calculations, which showed that 4f orbital bonding in CeLK4 has partial covalent character owing to ligand-to-metal charge transfer (LMCT) in the ground state. The experimental results are presented in the context of earlier measurements on tetravalent cerium compounds, indicating that the amount LMCT for CeLK4 is similar to that observed for [Et4N]2[CeCl6] and CeO2, and significantly less than that for the organometallic sandwich compound cerocene, (C8H8)2Ce. A simple model to rationalize changes in 4f orbitals for tri-and tetravalent lanthanide and actinide compounds is also provided.

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3dx-ray-absorption lines and the 3d94fn+1multiplets of

Cited by 735 publications

References 37 publications

Exchange Interaction of Strongly Anisotropic Tripodal Erbium Single-Ion Magnets with Metallic Surfaces

Exchange Interaction of Strongly Anisotropic Tripodal Erbium Single-Ion Magnets with Metallic Surfaces

Retracted Article: On the enzymatic activity of catalase: an iron L-edge X-ray absorption study of the active centre

A Macrocyclic Chelator That Selectively Binds Ln⁴⁺ over Ln³⁺ by a Factor of 10²⁹

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3dx-ray-absorption lines and the 3d94fn+1multiplets of

Cited by 735 publications

References 37 publications

Exchange Interaction of Strongly Anisotropic Tripodal Erbium Single-Ion Magnets with Metallic Surfaces

Exchange Interaction of Strongly Anisotropic Tripodal Erbium Single-Ion Magnets with Metallic Surfaces

Retracted Article: On the enzymatic activity of catalase: an iron L-edge X-ray absorption study of the active centre

A Macrocyclic Chelator That Selectively Binds Ln4+ over Ln3+ by a Factor of 1029

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A Macrocyclic Chelator That Selectively Binds Ln⁴⁺ over Ln³⁺ by a Factor of 10²⁹