Resonant soft X-ray Raman scattering of NiO

Resonant soft X-ray Raman scattering measurements on NiO have been made at photon energies across the Ni 2p absorption edges. The details of the spectral features are identified as Raman scattering due to d-d and charge-transfer excitations. The spectra are interpreted within the single impurity Anderson model, including multiplets, crystal-field and charge-transfer effects. At threshold excitation, the spectral features consists of triplet-triplet and triplet-singlet transitions of the 3d8 configuration. For excitation energies corresponding to the charge-transfer region in the Ni 2p X-ray absorption spectrum of NiO, the emission spectra are instead dominated by charge-transfer transitions to the 3d9L-1 final state. Comparisons of the final states with other spectroscopical techniques are also made.Comment: 9 pages, 2 figures, 2 tables, http://iopscience.iop.org/0953-8984/14/13/32

Electronic structure investigation of Ti3AlC2, Ti3SiC2, and Ti3GeC2 by soft-X-ray emission spectroscopy

The electronic structures of epitaxially grown films of Ti3AlC2, Ti3SiC2 and Ti3GeC2 have been investigated by bulk-sensitive soft X-ray emission spectroscopy. The measured high-resolution Ti L, C K, Al L, Si L and Ge M emission spectra are compared with ab initio density-functional theory including core-to-valence dipole matrix elements. A qualitative agreement between experiment and theory is obtained. A weak covalent Ti-Al bond is manifested by a pronounced shoulder in the Ti L-emission of Ti3AlC2. As Al is replaced with Si or Ge, the shoulder disappears. For the buried Al and Si-layers, strongly hybridized spectral shapes are detected in Ti3AlC2 and Ti3SiC2, respectively. As a result of relaxation of the crystal structure and the increased charge-transfer from Ti to C, the Ti-C bonding is strengthened. The differences between the electronic structures are discussed in relation to the bonding in the nanolaminates and the corresponding change of materials properties.Comment: 15 pages, 8 figure

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_

Electronic structure investigation of CoO by means of soft X-ray scattering

The electronic structure of CoO is studied by resonant inelastic soft X-ray scattering spectroscopy using photon energies across the Co 2p absorption edges. The different spectral contributions from the energy-loss structures are identified as Raman scattering due to d-d and charge-transfer excitations. For excitation energies close to the L3 resonance, the spectral features are dominated by quartet-quartet and quartet-doublet transitions of the 3d7 configuration. At excitation energies corresponding to the satellites in the Co 2p X-ray absorption spectrum of CoO, the emission features are instead dominated by charge-transfer transitions to the 3d8L-1 final state. The spectra are interpreted and discussed with the support of simulations within the single impurity Anderson model with full multiplet effects which are found to yield consistent spectral functions to the experimental data.Comment: 8 pages, 2 figures, 2 tables, http://link.aps.org/doi/10.1103/PhysRevB.65.20510

The role of pre-school quality in promoting resilience in the cognitive development of young children

The study reported here investigates the role of pre-school education as a protective factor in the development of children who are at risk due to environmental and individual factors. This investigation builds upon earlier research by examining different kinds of 'quality' in early education and tests the hypothesis that pre-schools of high quality can moderate the impacts of risks upon cognitive development. Cognitive development was measured in 2857 English pre-schoolers at 36 and 58 months of age, together with 22 individual risks to children's development, and assessments were made of the quality of their pre-school provision. Multilevel Structural Equation Modelling revealed that: the global quality of pre-school can moderate the effects of familial risk (such as poverty); the relationships between staff and children can moderate the effects of child level risk (such as low birth weight); and the specific quality of curricular provision can moderate the effects of both. Policy makers need to take quality into account in their efforts to promote resilience in young 'at risk' children through early childhood services

101 Dothideomycetes genomes: A test case for predicting lifestyles and emergence of pathogens.

Dothideomycetes is the largest class of kingdom Fungi and comprises an incredible diversity of lifestyles, many of which have evolved multiple times. Plant pathogens represent a major ecological niche of the class Dothideomycetes and they are known to infect most major food crops and feedstocks for biomass and biofuel production. Studying the ecology and evolution of Dothideomycetes has significant implications for our fundamental understanding of fungal evolution, their adaptation to stress and host specificity, and practical implications with regard to the effects of climate change and on the food, feed, and livestock elements of the agro-economy. In this study, we present the first large-scale, whole-genome comparison of 101 Dothideomycetes introducing 55 newly sequenced species. The availability of whole-genome data produced a high-confidence phylogeny leading to reclassification of 25 organisms, provided a clearer picture of the relationships among the various families, and indicated that pathogenicity evolved multiple times within this class. We also identified gene family expansions and contractions across the Dothideomycetes phylogeny linked to ecological niches providing insights into genome evolution and adaptation across this group. Using machine-learning methods we classified fungi into lifestyle classes with >95 % accuracy and identified a small number of gene families that positively correlated with these distinctions. This can become a valuable tool for genome-based prediction of species lifestyle, especially for rarely seen and poorly studied species

Synthesis of the originally proposed structures of elatenyne and an enyne from Laurencia majuscula

A bidirectional synthesis of the originally proposed structures for the natural products elatenyne and a chloroenyne from Laurencia majuscula is described along with a reassessment of the structures of the halogenated enynes based upon a C-13 NMR chemical shift/structure correlation