Electronic Structure of Transition-Metal Dicyanamides Me[N(CN)2_2]2_2 (Me = Mn, Fe, Co, Ni, Cu)

The electronic structure of Me[N(CN)$_2$]$_2$ (Me=Mn, Fe, Co, Ni, Cu) molecular magnets has been investigated using x-ray emission spectroscopy (XES) and x-ray photoelectron spectroscopy (XPS) as well as theoretical density-functional-based methods. Both theory and experiments show that the top of the valence band is dominated by Me 3d bands, while a strong hybridization between C 2p and N 2p states determines the valence band electronic structure away from the top. The 2p contributions from non-equivalent nitrogen sites have been identified using resonant inelastic x-ray scattering spectroscopy with the excitation energy tuned near the N 1s threshold. The binding energy of the Me 3d bands and the hybridization between N 2p and Me 3d states both increase in going across the row from Me = Mn to Me = Cu. Localization of the Cu 3d states also leads to weak screening of Cu 2p and 3s states, which accounts for shifts in the core 2p and 3s spectra of the transition metal atoms. Calculations indicate that the ground-state magnetic ordering, which varies across the series is largely dependent on the occupation of the metal 3d shell and that structural differences in the superexchange pathways for different compounds play a secondary role.Comment: 20 pages, 11 figures, 2 table

Soft X-ray fluorescence study of the quasi-one dimensional Heisenberg antiferromagnet tetraphenylverdazyl

金沢大学理学部Soft-x-ray fluorescence measurements have been performed on a single crystal of the organic antiferromagnet 2,4,6-triphenylverdazyl. Resonant and nonresonant C Ka and N Ka (2p!1s transition! x-ray emission spectra ~XES! were measured and compared with x-ray photoelectron valence band spectra and deMon density-functional theory calculations. It is shown that intramolecular interactions are much stronger than intermolecular ones and give the main contribution to the formation of C 2p density of states. We present evidence of a delocalization of unpaired N 2p electrons over the verdazyl ring. The excitation energy dependence of C Ka and N Ka XES observed below the C 1s and N 1s thresholds, respectively, is discussed in terms of symmetry selective resonant inelastic x-ray scattering

Electronic structure of thiophenes and phthalocyanines

金沢大学理学部The results of x-ray fluorescence measurements of thiophenes @regioregular poly ~3-hexylthiophene ~P3HT! and a,v-dihexylquaterthiophene ~DHa4T!# and phtalocyanines @copper phtalocyanine ~CuPc! and copper hexadecafluorophtalocyanine (F16CuPc)# are presented. Experimental carbon, nitrogen, fluorine Ka and sulphur, copper L2,3 x-ray emission spectra are compared with ultraviolet photoemission spectroscopy spectra and deMon density-functional theory calculations of model molecules. We find that the carbon Ka emission is almost identical for P3HT and DHa4T. This indicates that the electronic structure of the p system is not affected by the presence of the side group. The ratio of emission intensities of the Cu L2 to Cu L3 intensities is found to be smaller by a factor of 2 for CuPc and F16CuPc than it is for pure metal. This demonstrates the strong covalency in phalocyanines

Photoemission study of the metal-insulator transition in CuIr2S4

We have studied the electronic structure and its changes across the metal-insulator transition in the spinel-type compound CuIr2S4 using photoemission and inverse-photoemission spectroscopy. Photoemission spectra near the Fermi level show a gap opening of ~20 meV in the insulating phase, consistent with the transport activation energy. Core-level spectra indicate that the Cu ion is monovalent, and hence Ir is in the intermediate valence state of +3.5. Comparison between the spectra and band-structure calculation reveals that the Ir 5d density of states is strongly distorted, probably due to electron correlation in spite of the general belief of weak correlation in 5d-electron systems

High Magnetic Field Behaviour of the Triangular Lattice Antiferromagnet, CuFeO_2

The high magnetic field behaviour of the triangular lattice antiferromagnet CuFeO_2 is studied using single crystal neutron diffraction measurements in a field of up to 14.5 T and also by magnetisation measurements in a field of up to 12 T. At low temperature, two well-defined first order magnetic phase transitions are found in this range of applied magnetic field (H // c): at H_c1=7.6(3)/7.1(3) T and H_c2=13.2(1)/12.7(1) T when ramping the field up/down. In a field above H_c2 the magnetic Bragg peaks show unusual history dependence. In zero field T_N1=14.2(1) K separates a high temperature paramagnetic and an intermediate incommensurate structure, while T_N2=11.1(3) K divides an incommensurate phase from the low-temperature 4-sublattice ground state. The ordering temperature T_N1 is found to be almost field independent, while T_N2 decreases noticeably in applied field. The magnetic phase diagram is discussed in terms of the interactions between an applied magnetic field and the highly frustrated magnetic structure of CuFeO_2Comment: 7 pages, 8 figures in ReVTeX. To appear in PR

Electronic structure of CuV2S4

The results of ab initio band-structure calculations and measurements of x-ray-emission valence spectra (XES) (Cu Lα, V Kβ5, V Lα, S Kβ1,3, S L2,3) and X-ray-photoelectron valence-band and core-level spectra (XPS) of CuV2S4 thiospinel are presented. It is found that a peak in valence-conduction bands close to the Fermi level is formed by V 3d states, which provide the metallic properties of CuV2S4. The valence band is formed by Cu 3d, V 3d, V 4p, and S 3p states. Examination of the XES and XPS results and the calculated charge-density maps and densities of states indicates that the valences of both Cu and V are similar to those of their elemental solids. Calculations show a strong electron-phonon coupling in CuV2S4 and the prospect of superconducting behavior has not been confirmed

Investigation of the thermal stability of Mg/Co periodic multilayers for EUV applications

We present the results of the characterization of Mg/Co periodic multilayers and their thermal stability for the EUV range. The annealing study is performed up to a temperature of 400\degree C. Images obtained by scanning transmission electron microscopy and electron energy loss spectroscopy clearly show the good quality of the multilayer structure. The measurements of the EUV reflectivity around 25 nm (~49 eV) indicate that the reflectivity decreases when the annealing temperature increases above 300\degreeC. X-ray emission spectroscopy is performed to determine the chemical state of the Mg atoms within the Mg/Co multilayer. Nuclear magnetic resonance used to determine the chemical state of the Co atoms and scanning electron microscopy images of cross sections of the Mg/Co multilayers reveal changes in the morphology of the stack from an annealing temperature of 305\degreee;C. This explains the observed reflectivity loss.Comment: Published in Applied Physics A: Materials Science \& Processing Published at http://www.springerlink.com.chimie.gate.inist.fr/content/6v396j6m56771r61/ 21 page

Electronic structure of a Mn12 molecular magnet: Theory and experiment

金沢大学大学院自然科学研究科物質情報解析We used site-selective and element-specific resonant inelastic x-ray scattering (RIXS) to study the electronic structure and the electron interaction effects in the molecular magnet [Mn12 O12 (C H3 COO)16 (H2 O)4] 2C H3 COOH 4 H2 O, and compared the experimental data with the results of local spin density approximation +U electron structure calculations which include the on-site Coulomb interactions. We found a good agreement between theory and experiment for the Coulomb repulsion parameter U=4 eV. In particular, the p-d band separation of 1.8 eV has been found from the RIXS spectra, which is in accordance with the calculations. Similarly, the positions of the peaks in the XPS spectra agree with the calculated densities of p and d states. Using the results of the electronic structure calculations, we determined the intramolecular exchange parameters, and used them for diagonalization of the Mn12 spin Hamiltonian. The calculated exchanges gave the correct ground state with the total spin S=10. © 2007 The American Physical Society