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

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

The contribution of environmental exposure to the etiology of autism spectrum disorder

Autism spectrum disorder (ASD) is a neurodevelopmental condition of heterogeneous etiology. While it is widely recognized that genetic and environmental factors and their interactions contribute to autism phenotypes, their precise causal mechanisms remain poorly understood. This article reviews our current understanding of environmental risk factors of ASD and their presumed adverse physiological mechanisms. It comprehensively maps the significance of parental age, teratogenic compounds, perinatal risks, medication, smoking and alcohol use, nutrition, vaccination, toxic exposures, as well as the role of extreme psychosocial factors. Further, we consider the role of potential protective factors such as folate and fatty acid intake. Evidence indicates an increased offspring vulnerability to ASD through advanced maternal and paternal age, valproate intake, toxic chemical exposure, maternal diabetes, enhanced steroidogenic activity, immune activation, and possibly altered zinc-copper cycles and treatment with selective serotonin reuptake inhibitors. Epidemiological studies demonstrate no evidence for vaccination posing an autism risk. It is concluded that future research needs to consider categorical autism, broader autism phenotypes, as well as autistic traits, and examine more homogenous autism variants by subgroup stratification. Our understanding of autism etiology could be advanced by research aimed at disentangling the causal and non-causal environmental effects, both founding and moderating, and gene-environment interplay using twin studies, longitudinal and experimental designs. The specificity of many environmental risks for ASD remains unknown and control of multiple confounders has been limited. Further understanding of the critical windows of neurodevelopmental vulnerability and investigating the fit of multiple hit and cumulative risk models are likely promising approaches in enhancing the understanding of role of environmental factors in the etiology of ASD.peerReviewe