Trapping of electrons near chemisorbed hydrogen on graphene

Chemical adsorption of atomic hydrogen on a negatively charged single layer graphene sheet has been analyzed with ab-initio Density Functional Theory calculations. We have simulated both finite clusters and infinite periodic systems to investigate the effect of different ingredients of the theory, e.g. exchange and correlation potentials, basis sets, etc. Hydrogen's electron affinity dominates the energetic balance in the charged systems and the extra electron is predominantly attracted to a region nearby the chemisorbed atom. The main consequences are: (i) the cancellation of the unpaired spin resulting in a singlet ground-state, and (ii) a stronger interaction between hydrogen and the graphene sheet.Comment: 11 pages, 8 figures, to be published in PR

Crystal structure and electronic states of tripotassium picene

The crystal structure of potassium doped picene with an exact stoichiometry (K3C22H14, K3picene from here onwards) has been theoretically determined within Density Functional Theory allowing complete variational freedom of the crystal structure parameters and the molecular atomic positions. A modified herringbone lattice is obtained in which potassium atoms are intercalated between two paired picene molecules displaying the two possible orientations in the crystal.Along the c-axis, organic molecules alternate with chains formed by three potassium atoms. The electronic structureof the doped material resembles pristine picene, except that now the bottom of the conduction band is occupied by six electrons coming from the ionized K atoms (six per unit cell). Wavefunctions remain based mainly on picene molecular orbitals getting their dispersion from intralayer edge to face CH/pi bonding, while eigenenergies have been modified by the change in the electrostatic potential. The small dispersion along the c-axis is assigned to small H-H overlap. From the calculated electronic density of states we expect metallic behavior for potassium doped picene.Comment: Published version: 8 twocolumn pages, 7 color figures, 2 structural .cif files include

Ab-initio calculation of the effect of stress on the chemical activity of graphene

Graphene layers are stable, hard, and relatively inert. We study how tensile stress affects $\sigma$ and $\pi$ bonds and the resulting change in the chemical activity. Stress affects more strongly $\pi$ bonds that can become chemically active and bind to adsorbed species more strongly. Upon stretch, single C bonds are activated in a geometry mixing $120^{o}$ and $90^{o}$; an intermediate state between $sp^{2}$ and $sp^{3}$ bonding. We use ab-initio density functional theory to study the adsorption of hydrogen on large clusters and 2D periodic models for graphene. The influence of the exchange-correlation functional on the adsorption energy is discussed

Patterson Function from Low-Energy Electron Diffraction Measured Intensities and Structural Discrimination

Surface Patterson Functions have been derived by direct inversion of experimental Low-Energy Electron Diffraction I-V spectra measured at multiple incident angles. The direct inversion is computationally simple and can be used to discriminate between different structural models. 1x1 YSi_2 epitaxial layers grown on Si(111) have been used to illustrate the analysis. We introduce a suitable R-factor for the Patterson Function to make the structural discrimination as objective as possible. From six competing models needed to complete the geometrical search, four could easily be discarded, achieving a very significant and useful reduction in the parameter space to be explored by standard dynamical LEED methods. The amount and quality of data needed for this analysis is discussed.Comment: 5 pages, 4 figure

Diffusion of Hydrogen in Pd Assisted by Inelastic Ballistic Hot Electrons

Sykes {\it et al.} [Proc. Natl. Acad. Sci. {\bf 102}, 17907 (2005)] have reported how electrons injected from a scanning tunneling microscope modify the diffusion rates of H buried beneath Pd(111). A key point in that experiment is the symmetry between positive and negative voltages for H extraction, which is difficult to explain in view of the large asymmetry in Pd between the electron and hole densities of states. Combining concepts from the theory of ballistic electron microscopy and electron-phonon scattering we show that H diffusion is driven by the $s$-band electrons only, which explains the observed symmetry.Comment: 5 pages and 4 figure

Quantum mechanical analysis of the elastic propagation of electrons in the Au/Si system: application to Ballistic Electron Emission Microscopy

We present a Green's function approach based on a LCAO scheme to compute the elastic propagation of electrons injected from a STM tip into a metallic film. The obtained 2D current distribution in real and reciprocal space furnish a good representation of the elastic component of Ballistic Electron Emission Microscopy (BEEM) currents. Since this component accurately approximates the total current in the near threshold region, this procedure allows --in contrast to prior analyses-- to take into account effects of the metal band structure in the modeling of these experiments. The Au band structure, and in particular its gaps appearing in the [111] and [100] directions provides a good explanation for the previously irreconcilable results of nanometric resolution and similarity of BEEM spectra on both Au/Si(111) and Au/Si(100).Comment: 12 pages, 9 postscript figures, revte

Allelic variation observed at one microsatellite locus between the two synonym grape cultivars Black Currant and Mavri Corinthiaki

Research NoteBlack Currant and Mavri Corinthiaki are considered synonyms for Corinthe Noir, a parthenocarpic seedless raisin cultivar. No differences between them were found by RAPD analysis with 1 1 primers. They also have the same genotype in 15 out of 16 microsatellite loci, demonstrating the Black Currant and Mavri Corinthiaki are essentially identical. Nevertheless, a difference was observed in one allele at one locus (VVMD7): the Black Currant genotype is 240:246 while the Mavri Corinthiaki genotype is 240:248. A mutation in the microsatellite sequence might be responsible for that difference. Possible consequences of such mutations are discussed

Integration of biophysical connectivity in the spatial optimization of coastal ecosystem services

Ecological connectivity in coastal oceanic waters is mediated by dispersion of the early life stages of marine organisms and conditions the structure of biological communities and the provision of ecosystem services. Integrated management strategies aimed at ensuring long-term service provision to society do not currently consider the importance of dispersal and larval connectivity. A spatial optimization model is introduced to maximise the potential provision of ecosystem services in coastal areas by accounting for the role of dispersal and larval connectivity. The approach combines a validated coastal circulation model that reproduces realistic patterns of larval transport along the coast, which ultimately conditions the biological connectivity and productivity of an area, with additional spatial layers describing potential ecosystem services. The spatial optimization exercise was tested along the coast of Central Chile, a highly productive area dominated by the Humboldt Current. Results show it is unnecessary to relocate existing management areas, as increasing no-take areas by 10% could maximise ecosystem service provision, while improving the spatial representativeness of protected areas and minimizing social conflicts. The location of protected areas was underrepresented in some sections of the study domain, principally due to the restriction of the model to rocky subtidal habitats. Future model developments should encompass the diversity of coastal ecosystems and human activities to inform integrative spatial management. Nevertheless, the spatial optimization model is innovative not only for its integrated ecosystem perspective, but also because it demonstrates that it is possible to incorporate time-varying biophysical connectivity within the optimization problem, thereby linking the dynamics of exploited populations produced by the spatial management regime.Comment: 30 pages, 5 figures, 2 tables; 1 graphical abstract. In this version: numbering of figures corrected, updated figure 2, typos corrected and references fixe