Highlights of the Science and Life of Peter Varga (1946—2018)

Peter Varga has passed on October 27, 2018. His pioneering discoveries of chemical resolution at the atomic scale on surface alloys, atomic resolution of ultrathin alkali halides, nucleation of bcc iron in ultrathin films, and the microscopic structure of ultrathin alumina films stimulated worldwide research. In recognition of his outstanding scientific contributions, in December 2017 the Japanese Society for the Promotion of Science (JSPS) awarded him a prize for his distinguished contribution on the clarification of surface phenomena by atomic level investigations and the development of novel functional materials. This contribution highlights the life of Peter Varga as a scientist and as a person. With his elegance, his energy, his wit, and his generosity he was a close friend and role model to many of us, and showed us how to combine scientific curiosity and creativity with the lightness of being

Does ursodeoxycholic acid change the proliferation of the colorectal mucosa? A randomized, placebo-controlled study

Background: In animal models ursodeoxycholic acid (UDCA) showed a chemoprotective effect against colon cancer. To explain this, a reduced proliferation of the colorectal mucosal proliferation was suggested. We, therefore, examined the influence of UDCA on the proliferation of normal colorectal mucosa in humans. Methods: Following endoscopic polypectomy, 20 patients with colorectal adenomas were randomized to receive either UDCA (750 mg/day, n = 10, group A) or placebo (n = 10, group B) for 6 months in a double-blinded way. Colorectal biopsies were sampled before and at the end of the medication by total colonoscopy. Colorectal mucosal proliferation was measured by FACScan analysis of propidium iodine labeling. Serum was sampled, and serum bile acids were analyzed by gas chromatography. Results: The proliferation rates at the end of the study were similar in both groups (median 15.4%; range 12.0-20.9 in group A; median 16.0%, 14.0-20.2 in group B, p = 0.41). Serum lithocholic acid levels at the end of the study were significantly higher in group A (1.3 mumol/l, 0.9-1.8) than in group B (0.7 mumol/l, 0-1.7, p < 0.02), whereas serum deoxycholic acid levels were similar in both groups. Conclusions: In this study, UDCA treatment for 6 months does not seem to induce changes in the proliferative behavior of the colorectal mucosa in patients with adenomas. It seems likely that a putative chemopreventive effect of UDCA in humans is not exerted by a reduction of the colorectal proliferation. Copyright (C) 2003 S. Karger AG, Basel

Unraveling CO adsorption on model single-atom catalysts

Understanding how the local environment of a "single-atom" catalyst affects stability and reactivity remains a challenge. We present an in-depth study of copper1, silver1, gold1, nickel1, palladium1, platinum1, rhodium1, and iridium1 species on Fe3O4(001), a model support in which all metals occupy the same twofold-coordinated adsorption site upon deposition at room temperature. Surface science techniques revealed that CO adsorption strength at single metal sites differs from the respective metal surfaces and supported clusters. Charge transfer into the support modifies the d-states of the metal atom and the strength of the metal-CO bond. These effects could strengthen the bond (as for Ag1-CO) or weaken it (as for Ni1-CO), but CO-induced structural distortions reduce adsorption energies from those expected on the basis of electronic structure alone. The extent of the relaxations depends on the local geometry and could be predicted by analogy to coordination chemistry

Novel electronic and magnetic properties of ultrathin chromium oxide films grown on Pt(111)

The growth of epitaxial metal–oxide films on lattice-mismatched metal substrates often results in the formation of unique overlayer structures. In particular, epitaxial chromium oxide films grown on Pt(111) exhibit a p(2×2) symmetry through the first two monolayers of growth which is followed by a (√3×√3)R30° phase that is attributed to the growth of a Cr2O3(0001) overlayer. Ultraviolet photoelectron spectroscopy measurements have been performed on the CrOx/Pt(111) system. The electronic structures of CrO2, Cr2O3, and Cr3O4 were calculated using the linear muffin-tin orbital method in the atomic sphere approximation. Comparison of the photoemission valence band spectra with the calculated density of states indicates that the CrOx initially grows in a cubic spinel Cr3O4 structure. Beyond ∼0.2 monolayers, the metallic behavior of the CrOx overlayer begins a transformation to an insulating state. The measured valence emission for the p(2×2) phase beyond ∼0.2 monolayers is more consistent with either a γ-Cr2O3(111) overlayer or possibly a reconstructed Cr2O3(0001) overlayer. © 1998 American Vacuum Society

H2S adsorption on chromium, chromia, and gold/chromia surfaces: Photoemission studies

The reaction of H2S with chromium, chromia, and Au/chromia films grown on a Pt(111) crystal has been investigated using synchrotron-based high-resolution photoemission spectroscopy. At 300 K, H2S completely decomposes on polycrystalline chromium producing a chemisorbed layer of S that attenuates the Cr 3d valence features. No evidence was found for the formation of CrSx species. The dissociation of H2S on Cr3O4 and Cr2O3 films at room temperature produces a decrease of 0.3–0.8 eV in the work function of the surface and significant binding-energy shifts (0.2–0.6 eV) in the Cr 3p core levels and Cr 3d features in the valence region. The rate of dissociation of H2S increases following the sequence: Cr2O33O4. For chromium, the density of states near the Fermi level is large, and these states offer a better match in energy for electron acceptor or donor interactions with the frontier orbitals of H2S than the valence and conduction bands of the chromium oxides. This leads to a large dissociation probability for H2S on the metal, and a low dissociation probability for the molecule on the oxides. In the case of Cr3O4 and Cr2O3, there is a correlation between the size of the band gap in the oxide and its reactivity toward H2S. The uptake of sulfur by the oxides significantly increases when they are “promoted” with gold. The Au/Cr2O3 surfaces exhibit a unique electronic structure in the valence region and a larger ability to dissociate H2S than polycrystalline Au or pure Cr2O3. The results of ab initio SCF calculations for the adsorption of H2S on AuCr4O6 and AuCr10O15 clusters show a shift of electrons from the gold toward the oxide unit that enhances the strength of the Au(6s)↔H2S(5a1,2b1) bonding interactions and facilitates the decomposition of the molecule. © 1997 American Institute of Physics

Structure and apparent topography of TiO2 (110) surfaces

We present self-consistent ab-initio total-energy and electronic-structure calculations on stoichiometric and non-stoichiometric TiO2 (110) surfaces. Scanning tunneling microscopy (STM) topographs are simulated by calculating the local electronic density of states over an energy window appropriate for the experimental positive-bias conditions. We find that under these conditions the STM tends to image the undercoordinated Ti atoms, in spite of the physical protrusion of the O atoms, giving an apparent reversal of topographic contrast on the stoichiometric 1x1 or missing-row 2x1 surface. We also show that both the interpretation of STM images and the direct comparison of surface energies favor an added-row structure over the missing-row structure for the oxygen-deficient 2x1 surface.Comment: 6 pages, two-column style with 5 postscript figures embedded. Uses REVTEX and epsf macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/index.html#ng_tio

Multiple shifts and fractional integration in the us and uk unemployment rates

This paper analyses the long-run behaviour of the US and UK unemployment rates by testing for possibly fractional orders of integration and multiple shifts using a sample of over 100 annual observations. The results show that the orders of integration are higher than 0 in both series, which implies long memory. If we assume that the underlying disturbances are white noise, the values are higher than 0.5, i.e., nonstationary. However, if the disturbances are autocorrelated, the orders of integration are in the interval (0, 0.5), implying stationarity and mean-reverting behaviour. Moreover, when multiple shifts are taken into account, unemployment is more persistent in the US than in the UK, implying the need for stronger policy action in the former to bring unemployment back to its original level

A Multitechnique Study of C2H4Adsorption on Fe3O4(001)

The adsorption/desorption of ethene (C2H4), also commonly known as ethylene, on Fe3O4(001) was studied under ultrahigh vacuum conditions using temperature-programmed desorption (TPD), scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT)-based computations. To interpret the TPD data, we have employed a new analysis method based on equilibrium thermodynamics. C2H4adsorbs intact at all coverages and interacts most strongly with surface defects such as antiphase domain boundaries and Fe adatoms. On the regular surface, C2H4binds atop surface Fe sites up to a coverage of 2 molecules per (√2 × √2)R45° unit cell, with every second Fe occupied. A desorption energy of 0.36 eV is determined by analysis of the TPD spectra at this coverage, which is approximately 0.1-0.2 eV lower than the value calculated by DFT + U with van der Waals corrections. Additional molecules are accommodated in between the Fe rows. These are stabilized by attractive interactions with the molecules adsorbed at Fe sites. The total capacity of the surface for C2H4adsorption is found to be close to 4 molecules per (√2 × √2)R45° unit cell

Non-stoichiometric oxide and metal interfaces and reactions

We have employed a combination of experimental surface science techniques and density functional calculations to study the reduction of TiO2(110) surfaces through the doping with submonolayer transition metals. We concentrate on the role of Ti adatoms in self doping of rutile and contrast the behaviour to that of Cr. DFT+U calculations enable identification of probable adsorption structures and their spectroscopic characteristics. Adsorption of both metals leads to a broken symmetry and an asymmetric charge transfer localised around the defect site of a mixed localised/delocalised character. Charge transfer creates defect states with Ti 3d character in the band gap at similar to 1-eV binding energy. Cr adsorption, however, leads to a very large shift in the valence-band edge to higher binding energy and the creation of Cr 3d states at 2.8-eV binding energy. Low-temperature oxidation lifts the Ti-derived band-gap states and modifies the intensity of the Cr features, indicative of a change of oxidation state from Cr3+ to Cr4+. Higher temperature processing leads to a loss of Cr from the surface region, indicative of its substitution into the bulk