Local adsorption structure and bonding of porphine on Cu(111) before and after self-metalation

We have experimentally determined the lateral registry and geometric structure of free-base porphine (2H-P) and copper-metalated porphine (Cu-P) adsorbed on Cu(111), by means of energy-scanned photoelectron diffraction (PhD), and compared the experimental results to density functional theory (DFT) calculations that included van der Waals corrections within the Tkatchenko-Scheffler approach. Both 2H-P and Cu-P adsorb with their center above a surface bridge site. Consistency is obtained between the experimental and DFT-predicted structural models, with a characteristic change in the corrugation of the four N atoms of the molecule's macrocycle following metalation. Interestingly, comparison with previously published data for cobalt porphine adsorbed on the same surface evidences a distinct increase in the average height of the N atoms above the surface through the series 2H-P, Cu-P, cobalt porphine. Such an increase strikingly anti-correlates the DFT-predicted adsorption strength, with 2H-P having the smallest adsorption height despite the weakest calculated adsorption energy. In addition, our findings suggest that for these macrocyclic compounds, substrate-to-molecule charge transfer and adsorption strength may not be univocally correlated

Evidence for Strong Itinerant Spin Fluctuations in the Normal State of CeFeAsO(0.89)F(0.11) Iron-Oxypnictides

The electronic structure in the normal state of CeFeAsO0.89F0.11 oxypnictide superconductors has been investigated with x-ray absorption and photoemission spectroscopy. All the data exhibit signatures of Fe d-electron itinerancy. Exchange multiplets appearing in the Fe 3s core level indicate the presence of itinerant spin fluctuations. These findings suggest that the underlying physics and the origin of superconductivity in these materials are likely to be quite different from those of the cuprate high-temperature superconductors. These materials provide opportunities for elucidating the role of magnetic fluctuations in high-temperature superconductivity.Comment: Shorter version. Accepted in Phys. Rev. Let

The momentum and photon energy dependence of the circular dichroic photoemission in the bulk Rashba semiconductors BiTeX (X = I, Br, Cl)

Bulk Rashba systems BiTeX (X = I, Br, Cl) are emerging as important candidates for developing spintronics devices, because of the coexistence of spin-split bulk and surface states, along with the ambipolar character of the surface charge carriers. The need of studying the spin texture of strongly spin-orbit coupled materials has recently promoted circular dichroic Angular Resolved Photoelectron Spectroscopy (cd-ARPES) as an indirect tool to measure the spin and the angular degrees of freedom. Here we report a detailed photon energy dependent study of the cd-ARPES spectra in BiTeX (X = I, Br and Cl). Our work reveals a large variation of the magnitude and sign of the dichroism. Interestingly, we find that the dichroic signal modulates differently for the three compounds and for the different spin-split states. These findings show a momentum and photon energy dependence for the cd-ARPES signals in the bulk Rashba semiconductor BiTeX (X = I, Br, Cl). Finally, the outcome of our experiment indicates the important relation between the modulation of the dichroism and the phase differences between the wave-functions involved in the photoemission process. This phase difference can be due to initial or final state effects. In the former case the phase difference results in possible interference effects among the photo-electrons emitted from different atomic layers and characterized by entangled spin-orbital polarized bands. In the latter case the phase difference results from the relative phases of the expansion of the final state in different outgoing partial waves.Comment: 6 pages, 4 figure

Electronic Structure of CeFeAsO1-xFx (x=0, 0.11/x=0.12) compounds

We report an extensive study on the intrinsic bulk electronic structure of the high-temperature superconductor CeFeAsO0.89F0.11 and its parent compound CeFeAsO by soft and hard x-ray photoemission, x-ray absorption and soft-x-ray emission spectroscopies. The complementary surface/bulk probing depth, and the elemental and chemical sensitivity of these techniques allows resolving the intrinsic electronic structure of each element and correlating it with the local structure, which has been probed by extended-x-ray absorption fine structure spectroscopy. The measurements indicate a predominant 4f1 (i.e. Ce3+) initial state configuration for Cerium and an effective valence-band-to-4f charge-transfer screening of the core hole. The spectra also reveal the presence of a small Ce f0 initial state configuration, which we assign to the occurrence of an intermediate valence state. The data reveal a reasonably good agreement with the partial density of states as obtained in standard density functional calculations over a large energy range. Implications for the electronic structure of these materials are discussed.Comment: Accepted for publication in Phys. Rev.

Structural investigation of the Rh(110)-c(2x2)-CN phase

The Rh(110)-c(2x2)-CN phase has been examined by means of scanning tunneling microscopy (STM) and full dynamical low-energy electron diffraction (LEED). From STM large c(2x2) domains are observed. The detailed LEED-IV structural analysis indicates that CN is located in the grooves of the (110) surface, approximately atop second layer rhodium atoms. The CN molecules lie almost flat with their bond axes oriented perpendicular to the rhodium troughs. An outward relaxation of the first substrate interlayer distance and a strong buckling of the second Rh layer are induced by CN adsorption. Calculated and experimental intensity curves are in good agreement. An exhaustive set of other possible adsorption sites and configurations was tested and excluded on the basis of reliability-factor analysis

Experimental investigation of the electronic structure of Gd5Si2Ge2 by photoemission and x-ray absorption spectroscopy

The electronic structure of the magnetic refrigerant Gd5Ge2Si2 has been experimentally investigated by photoemission and x-ray absorption spectroscopy. The resonant photoemission and x-ray absorption measurements performed across the Gd N4,5 and Gd M4,5 edges identify the position of Gd 4f multiplet lines, and assess the 4f occupancy (4f7) and the character of the states close to the Fermi edge. The presence of Gd 5d states in the valence band suggests that an indirect 5d exchange mechanism underlies the magnetic interactions between Gd 4f moments in Gd5Ge2Si2. From 175 to 300 K the first 4 eV of the valence band and the Gd partial density of states do not display clear variations. A significant change is instead detected in the photoemission spectra at higher binding energy, around 5.5 eV, likely associated to the variation of the bonding and antibonding Ge(Si) s bands across the phase transition

Evidence for strong f -d hybridization in intermetallic ferromagnet CePdIn2

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