Photoemission investigation of the electronic structure of Fe-Pd and Fe-Pt alloys

A photoemission investigation of Fe-Pd and Fe-Pt transition-metal alloys, using ∼50–150-eV synchrotron radiation, is presented. We consider in particular the spectral distribution of Fe states when approaching the dilute limit. By means of the Cooper minimum in the 4d and 5d photoionization cross section, we identify structures that have mainly Fe minority- or Fe majority-spin character. The relative position of these peaks is discussed in terms of the covalent interaction between Fe 3d and Pd or Pt d states. Also, the strong resemblance between the distribution of Fe states in the Pd-based and in the Pt-based alloys is demonstrated. We find a consistent behavior of interacting d states towards the dilute limit. It is concluded that the Fe states that are observed in the photoemission spectra of the dilute alloys have mainly majority-spin character and are, because of the covalent interaction with host states, widely distributed over the energy range of the host d band. The Fe minority-spin band, which is centered near the Fermi level, gradually empties with increasing Fe dilution

Eukaryotic initiation factor-4E in superficial and muscle invasive bladder cancer and its correlation with vascular endothelial growth factor expression and tumour progression

Vascular endothelial growth factor (VEGF) is an important factor mediating tumour angiogenesis. VEGF mRNA is differentially expressed in bladder cancer with high expression in superficial tumours (stage pTaand pT1) contrasting with low expression in muscle invasive tumours (stage ≥ pT2). To investigate mechanisms regulating VEGF expression in bladder cancer, VEGF mRNA and protein were measured in normal bladder (n = 12) and primary bladder cancers (n = 57). VEGF protein levels correlated with mRNA expression in normal bladder (r = 0.68, P = 0.02) and bladder cancer (r = 0.46, P = 0.0007). Whilst VEGF mRNA expression was threefold higher in superficial compared to muscle invasive bladder cancers (P = 0.0001) there was no difference in VEGF protein (P = 0.81). Accordingly, the median protein:mRNA ratios increased more than 15-fold with increasing tumour stage (P< 0.0001) suggesting translational regulation. Expression of the eukaryotic initiation factor-4E (eIF-4E), a factor implicated in the translational regulation of VEGF, was greater in tumours than normal bladder (P< 0.0001) and correlated with VEGF protein:mRNA ratios (n = 43, r = 0.54, P = 0.0004) pointing to its role in the regulation of VEGF. In superficial tumours (n = 37) high expression of eIF-4E was associated with a poor prognosis and reduced stage progression-free survival (P = 0.04, Cox proportional hazards model). The study demonstrates that eIF-4E may be involved in translational regulation of VEGF in bladder cancer and might have a role as a prognostic factor in bladder cancer. © 2000 Cancer Research Campaig

Depletion of density of states near Fermi energy induced by disorder and electron correlation in alloys

We have performed high resolution photoemission study of substitutionally disordered alloys Cu-Pt, Cu-Pd, Cu-Ni, and Pd-Pt. The ratios between alloy spectra and pure metal spectra are found to have dips at the Fermi level when the residual resistivity is high and when rather strong repulsive electron-electron interaction is expected. This is in accordance with Altshuler and Aronov's model which predicts depletion of density of states at the Fermi level when both disorder and electron correlation are present.Comment: 1 tex file and 4 ps file

Reversibility of Ferri-/Ferrocyanide Redox during Operando Soft X-ray Spectroscopy

The ferri-/ferrocyanide redox couple is ubiquitous in many fields of physical chemistry. We studied its photochemical response to intense synchrotron radiation by in situ X-ray absorption spectroscopy (XAS). For photon flux densities equal to and above 2 × 1011 s–1 mm–2, precipitation of ferric (hydr)oxide from both ferricyanide and ferrocyanide solutions was clearly detectable, despite flowing fast enough to replace the solution in the flow cell every 0.4 s (flow rate 1.5 mL/min). During cyclic voltammetry, precipitation of ferric (hydr)oxide was promoted at reducing voltages and observed below 1011 s–1 mm–2. This was accompanied by inhibition of the ferri-/ferrocyanide redox, which we probed by time-resolved operando XAS. Our study highlights the importance of considering both electrochemical and spectroscopic conditions when designing in situ experiments

Resonant Auger spectroscopy at the L2,3 shake-up thresholds as a probe of electron correlation effects in nickel

The excitation energy dependence of the three-hole satellites in the L3-M4,5M4,5 and L2-M4,5M4,5 Auger spectra of nickel metal has been measured using synchrotron radiation. The satellite behavior in the non-radiative emission spectra at the L3 and L2 thresholds is compared and the influence of the Coster-Kronig channel explored. The three-hole satellite intensity at the L3 Auger emission line reveals a peak structure at 5 eV above the L3 threshold attributed to resonant processes at the 2p53d9 shake-up threshold. This is discussed in connection with the 6-eV feature in the x-ray absorption spectrum.Comment: 8 pages, 4 figures; http://prb.aps.org/abstract/PRB/v58/i7/p3677_

Correlated local distortions of the TlO layers in Tl2_2Ba2_2CuOy_{y}: An x-ray absorption study

We have used the XAFS (x-ray-absorption fine structure) technique to investigate the local structure about the Cu, Ba, and Tl atoms in orthorhombic Tl-2201 with a superconducting transition temperature T$_c$=60 K. Our results clearly show that the O(1), O(2), Cu, and Ba atoms are at their ideal sites as given by the diffraction measurements, while the Tl and O(3) atoms are more disordered than suggested by the average crystal structure. The Tl-Tl distance at 3.5 \AA{ } between the TlO layers does not change, but the Tl-Tl distance at 3.9 \AA{ } within the TlO layer is not observed and the Tl-Ba and Ba-Tl peaks are very broad. The shorter Tl-O(3) distance in the TlO layer is about 2.33 \AA, significantly shorter than the distance calculated with both the Tl and O(3) atoms at their ideal $4e$ sites ( $x=y=$0 or $\frac{1}{2}$). A model based on these results shows that the Tl atom is displaced along the directions from its ideal site by about 0.11 \AA; the displacements of neighboring Tl atoms are correlated. The O(3) atom is shifted from the $4e$ site by about 0.53 \AA{ } roughly along the directions. A comparison of the Tl L$_{III}$-edge XAFS spectra from three samples, with T$_c$=60 K, 76 K, and 89 K, shows that the O environment around the Tl atom is sensitive to T$_c$ while the Tl local displacement is insensitive to T$_c$ and the structural symmetry. These conclusions are compared with other experimental results and the implications for charge transfer and superconductivity are discussed. This paper has been submitted to Phys. Rev. B.Comment: 20 pages plus 14 ps figures, REVTEX 3.

Photoabsorption and photoion spectroscopy of atomic uranium in the region of 6p and 5d excitations

The photoabsorption process in atomic uranium has been investigated experimentally and theoretically in the 15–150-eV region. Using the dual laser plasma technique, the 6p photoabsorption spectrum has been recorded while for the first time the 5d region has been remeasured photoelectrically using both photoabsorption and photoion spectroscopy. Interpretation of the photoabsorption spectra is supported by Hartree-Fock calculations which take into account spin-flip decay and the interaction of many discrete states with many continua. The 6p spectrum is entirely dominated by spin-orbit split 6p⃗6d transitions. The 5d-subshell photoabsorption is shown to consist predominantly of discrete 5d⃗5f excitations; here the electrostatic and spin-orbit interactions are comparable in strength