A comparative study of density functional and density functional tight binding calculations of defects in graphene

The density functional tight binding approach (DFTB) is well adapted for the study of point and line defects in graphene based systems. After briefly reviewing the use of DFTB in this area, we present a comparative study of defect structures, energies and dynamics between DFTB results obtained using the dftb+ code, and density functional results using the localised Gaussian orbital code, AIMPRO. DFTB accurately reproduces structures and energies for a range of point defect structures such as vacancies and Stone-Wales defects in graphene, as well as various unfunctionalised and hydroxylated graphene sheet edges. Migration barriers for the vacancy and Stone-Wales defect formation barriers are accurately reproduced using a nudged elastic band approach. Finally we explore the potential for dynamic defect simulations using DFTB, taking as an example electron irradiation damage in graphene

Graphene edge structures: Folding, scrolling, tubing, rippling and twisting

Conventional three-dimensional crystal lattices are terminated by surfaces, which can demonstrate complex rebonding and rehybridisation, localised strain and dislocation formation. Two dimensional crystal lattices, of which graphene is the archetype, are terminated by lines. The additional available dimension at such interfaces opens up a range of new topological interface possibilities. We show that graphene sheet edges can adopt a range of topological distortions depending on their nature. Rehybridisation, local bond reordering, chemical functionalisation with bulky, charged, or multi-functional groups can lead to edge buckling to relieve strain, folding, rolling and even tube formation. We discuss the topological possibilities at a 2D graphene edge, and under what circumstances we expect different edge topologies to occur. Density functional calculations are used to explore in more depth different graphene edge types.Comment: Additional figure in published versio

Bromination of Graphene and Graphite

We present a density functional theory study of low density bromination of graphene and graphite, finding significantly different behaviour in these two materials. On graphene we find a new Br2 form where the molecule sits perpendicular to the graphene sheet with an extremely strong molecular dipole. The resultant Br+-Br- has an empty pz-orbital located in the graphene electronic pi-cloud. Bromination opens a small (86meV) band gap and strongly dopes the graphene. In contrast, in graphite we find Br2 is most stable parallel to the carbon layers with a slightly weaker associated charge transfer and no molecular dipole. We identify a minimum stable Br2 concentration in graphite, finding low density bromination to be endothermic. Graphene may be a useful substrate for stabilising normally unstable transient molecular states

Première découverte d'un Arthrodire (Placodermi, Vertebrata) dans le Dévonien d'Amérique du Sud

Des plaques dermiques d'un grand Arthrodire eubrachyhtoracide (Placodermi, Vertebrata), provisoirement attribuées à un Dunkleosteidae, ont été découvertes dans les faciès détritique de la Formation de Colpacucho (Famennien), sur la Péninsule de Cumana (Lac Titicaca, Bolivie). Il s'agit de la première découverte de restes d'Arthrodires en Amérique du Sud. Ces plaques d'Arthrodire sont associées à une épine de Chondrichthyen évoquant certaines espèces de "Ctenacanthus" du Famennien et du Carbonifère inférieur (Résumé d'auteur

Behavior of hydrogen ions, atoms, and molecules in a-boron studied using density functional calculations

We examine the behavior of hydrogen ions, atoms, and molecules in a-boron using density functionalcalculations. Hydrogen behaves as a negative-U center, with positive H ions preferring to sit off-center oninterlayer bonds and negative H ions sitting preferably at in-plane sites between three B12 icosahedra. Hydrogen atoms inside B12 icosahedral cages are unstable, drifting off-center and leaving the cage with only a 0.09 eV barrier. While H0 is extremely mobile (diffusion barrier 0.25 eV), H+ and H- have higher diffusion barriers of 0.9 eV. Once mobile, these defects will combine, forming H2 in the interstitial void space, which will remain trapped in the lattice until high temperatures. Based on these results we discuss potential differences for hydrogen behavior in -boron and compare with experimental muon-implantation data

First-Principles Study of Substitutional Metal Impurities in Graphene: Structural, Electronic and Magnetic Properties

We present a theoretical study using density functional calculations of the structural, electronic and magnetic properties of 3d transition metal, noble metal and Zn atoms interacting with carbon monovacancies in graphene. We pay special attention to the electronic and magnetic properties of these substitutional impurities and found that they can be fully understood using a simple model based on the hybridization between the states of the metal atom, particularly the d shell, and the defect levels associated with an unreconstructed D3h carbon vacancy. We identify three different regimes associated with the occupation of different carbon-metal hybridized electronic levels: (i) bonding states are completely filled for Sc and Ti, and these impurities are non-magnetic; (ii) the non-bonding d shell is partially occupied for V, Cr and Mn and, correspondingly, these impurties present large and localized spin moments; (iii) antibonding states with increasing carbon character are progressively filled for Co, Ni, the noble metals and Zn. The spin moments of these impurities oscillate between 0 and 1 Bohr magnetons and are increasingly delocalized. The substitutional Zn suffers a Jahn-Teller-like distortion from the C3v symmetry and, as a consequence, has a zero spin moment. Fe occupies a distinct position at the border between regimes (ii) and (iii) and shows a more complex behavior: while is non-magnetic at the level of GGA calculations, its spin moment can be switched on using GGA+U calculations with moderate values of the U parameter.Comment: 13 figures, 4 tables. Submitted to Phys. Rev. B on September 26th, 200

Solar Coronal Loops Associated with Small-scale Mixed Polarity Surface Magnetic Fields

How and where are coronal loops rooted in the solar lower atmosphere? The details of the magnetic environment and its evolution at the footpoints of coronal loops are crucial to understanding the processes of mass and energy supply to the solar corona. To address the above question, we use high-resolution line-of-sight magnetic field data from the Imaging Magnetograph eXperiment instrument on the SUNRISE balloon-borne observatory and coronal observations from the Atmospheric Imaging Assembly onboard the Solar Dynamics Observatory of an emerging active region. We find that the coronal loops are often rooted at the locations with minor small-scale but persistent opposite-polarity magnetic elements very close to the larger dominant polarity. These opposite-polarity small-scale elements continually interact with the dominant polarity underlying the coronal loop through flux cancellation. At these locations we detect small inverse Y-shaped jets in chromospheric Ca II H images obtained from the SUNRISE Filter Imager during the flux cancellation. Our results indicate that magnetic flux cancellation and reconnection at the base of coronal loops due to mixed polarity fields might be a crucial feature for the supply of mass and energy into the corona.Comment: Published in the Astrophysical Journal Supplement Serie

Kinematics of Magnetic Bright Features in the Solar Photosphere

Convective flows are known as the prime means of transporting magnetic fields on the solar surface. Thus, small magnetic structures are good tracers of the turbulent flows. We study the migration and dispersal of magnetic bright features (MBFs) in intergranular areas observed at high spatial resolution with Sunrise/IMaX. We describe the flux dispersal of individual MBFs as a diffusion process whose parameters are computed for various areas in the quiet Sun and the vicinity of active regions from seeing-free data. We find that magnetic concentrations are best described as random walkers close to network areas (diffusion index, gamma=1.0), travelers with constant speeds over a supergranule (gamma=1.9-2.0), and decelerating movers in the vicinity of flux emergence and/or within active regions (gamma=1.4-1.5). The three types of regions host MBFs with mean diffusion coefficients of 130 km^2/s, 80-90 km^2/s, and 25-70 km^2/s, respectively. The MBFs in these three types of regions are found to display a distinct kinematic behavior at a confidence level in excess of 95%.Comment: 8 pages, 4 figure

Pulsed thermal treatment of carbon up to 3000 °C using an atomic absorption spectrometer

An atomic absorption spectrometer unit fitted with a graphite furnace module is used to perform high temperature treatment on three carbonized polymers: polyvinyl chloride (PVC), polyvinylidene chloride (PVDC) and polyacrylonitrile (PAN). Using short pulses up to 45 s, we heat small samples to a maximum of 3000 °C. High-resolution transmission electron microscopy and X-ray diffractometry are used to track the growth of crystallites in the materials as a function of the heating temperature. We observe the well-known behaviour of large crystalline graphite growth in PVC-derived samples and the formation of curved graphitic layers in PVDC- and PAN-derived samples. This graphite furnace atomic absorption spectrometer approach is an attractive alternative to conventional laboratory-scale graphite furnaces in research of high temperature treatment of carbon and other refractory materials

Platinum and palladium on carbon nanotubes:Experimental and theoretical studies

<p>Pristine and oxygen plasma functionalised carbon nanotubes (CNTs) were studied after the evaporation of Pt and Pd atoms. High resolution transmission electron microscopy shows the formation of metal nanoparticles at the CNT surface. Oxygen functional groups grafted by the plasma functionalization act as nucleation sites for metal nanoparticles. Analysis of the C1s core level spectra reveals that there is no covalent bonding between the Pt or Pd atoms and the CNT surface. Unlike other transition metals such as titanium and copper, neither Pd nor Pt show strong oxygen interaction or surface oxygen scavenging behaviour. (C) 2013 Elsevier B.V. All rights reserved.</p>