Rings sliding on a honeycomb network: Adsorption contours, interactions, and assembly of benzene on Cu(111)

Using a van der Waals density functional (vdW-DF) [Phys. Rev. Lett. 92, 246401 (2004)], we perform ab initio calculations for the adsorption energy of benzene (Bz) on Cu(111) as a function of lateral position and height. We find that the vdW-DF inclusion of nonlocal correlations (responsible for dispersive interactions) changes the relative stability of eight binding-position options and increases the binding energy by over an order of magnitude, achieving good agreement with experiment. The admolecules can move almost freely along a honeycomb web of "corridors" passing between fcc and hcp hollow sites via bridge sites. Our diffusion barriers (for dilute and two condensed adsorbate phases) are consistent with experimental observations. Further vdW-DF calculations suggest that the more compact (hexagonal) Bz-overlayer phase, with lattice constant a = 6.74 \AA, is due to direct Bz-Bz vdW attraction, which extends to ~8 \AA. We attribute the second, sparser hexagonal Bz phase, with a = 10.24 \AA, to indirect electronic interactions mediated by the metallic surface state on Cu(111). To support this claim, we use a formal Harris-functional approach to evaluate nonperturbationally the asymptotic form of this indirect interaction. Thus, we can account well for benzene self-organization on Cu(111).Comment: 13 pages, 7 figures, 3 tables, submitted for publication Accepted for publication in Phys. Rev. B. This version contains improved notation (with corresponding relabeling of figures), very small corrections to some tabulated values, and corrections concerning lattice lengths and subsequent discussion of commensurability of unit-cell dimension

Response of the Shockley surface state to an external electrical field: A density-functional theory study of Cu(111)

The response of the Cu(111) Shockley surface state to an external electrical field is characterized by combining a density-functional theory calculation for a slab geometry with an analysis of the Kohn-Sham wavefunctions. Our analysis is facilitated by a decoupling of the Kohn-Sham states via a rotation in Hilbert space. We find that the surface state displays isotropic dispersion, quadratic until the Fermi wave vector but with a significant quartic contribution beyond. We calculate the shift in energetic position and effective mass of the surface state for an electrical field perpendicular to the Cu(111) surface; the response is linear over a broad range of field strengths. We find that charge transfer occurs beyond the outermost copper atoms and that accumulation of electrons is responsible for a quarter of the screening of the electrical field. This allows us to provide well-converged determinations of the field-induced changes in the surface state for a moderate number of layers in the slab geometry.Comment: 11 pages, 6 figures, 4 tables; accepted for publication by Phys. Rev. B; changes from v1 in response to referee comments, esp. to Sections I and V.B (inc. Table 4), with many added references, but no change in results or conclusion

Traitement de lixiviats stabilisés de décharge par des membranes de nanofiltration

Le terme "lixiviat" ou "jus de décharge", désigne l'eau qui a percolé à travers les déchets en se chargeant de polluants. Ces effluents pollués doivent être traités.En raison des exigences croissantes des normes de rejet et de la stabilisation des lixiviats au cours du temps, de nouvelles techniques ont fait leur apparition dans ce domaine. La technologie de l'osmose inverse s'est développée dans de nombreux pays européens. Cependant cette technique sélective et coûteuse, se justifie seulement quand les normes sont drastiques. C'est pourquoi la nanofiltration pourrait constituer une solution intermédiaire.L'objectif de ce travail est de contribuer à mieux maîtriser cette technique pour l'élimination de la Demande Chimique en Oxygène (DCO) récalcitrante, subsistant après les traitements biologiques classiques.Nous avons évalué les performances de trois membranes (organiques et minérales) pour l'abaissement de la charge organique, en fonction des conditions hydrodynamiques (vitesse et pression).Chacune de ces membranes possède un comportement spécifique vis à vis de ces lixiviats stabilisés (adsorption, polarisation de concentration, obstruction des pores).L'influence d'une coagulation préalable sur les performances d'épuration a également été examinée pour l'une des membranes.Cette étude constitue une étape préliminaire au dimensionnement d'une installation.Landfill leachate is the name given to water that has passed through solid waste and contains organic and mineral contaminants. Therefore this effluent must be treated before discharge to the environment. Because of new norms and the stabilization of leachates with time, new treatment methods have been designed. Thus, reverse osmosis is used in many European countries. But the use of reverse osmosis is only justified when norms are severe, because the treatment is highly selective (salt rejection >99%) and very expensive. In other cases, nanofiltration may be an interesting alternative.The purpose of the present work is to propose a process for recalcitrant organic matter in order to optimize the technique. Thus, three membranes (organic and mineral) have been used to evaluate their ability to decrease the Chemical Oxygen Demand (COD) of the leachate. This study helps to determine the size of the device. First, physical parameters were investigated. Each time, the hydraulic regime was turbulent (Re > 2500). Higher permeation fluxes were obtained with organic membranes than with the mineral one (80 L·h-1·m-2 compared to 25 L·h-1·m-2) under the same experimental conditions (10 bar and 3.4 m·s-1). Tangential flow rates higher than 2.5 m·s-1 do not influence COD retention; at lower flow rates polarisation concentration may occur. The removal of COD is achieved in the three cases. At 10 bar an acceptable value of less than 120 mg O2·L-1 (norm) is obtained. The inorganic membrane (Tech-Sep) gives the best results (COD rejection: 70 % at 10 bar).Membranes behave differently toward landfill. The organic membrane MP 20 (Weizmann membrane, cut-off 450 Dalton (Da), polyacrylonitrile) shows low adsorption with landfill leachate. The organic membrane MP 31 (Weizmann membrane, cut off 450 Da, polysulfone) gave a high COD retention ratio; the values for irreversible fouling and static adsorption are of the same order ofmagnitude; a strong membrane-foulant interaction must occur, which improves membrane selectivity. The mineral membrane N01A (Tech-Sep membrane, cut off 1000 Da, zirconium oxide), like MP-31, gives high static adsorption with leachate and irreversible fouling as well. The latter phenomenon can be explained by the obstruction of membrane pores by leachate particles, the size of which is near the membrane cut-off point. Fouling and static adsorption contribute to the increase in the membrane rejection rate. We studied coagulation as a pretreatment to improve performances of the N01A membrane. Experiments have been carried out with Jar-Test and FeCl3-like coagulants. The optimal amount of coagulant was 1.4 g Fe·L-1; 60% COD reduction was achieved. The results obtained with the N01A membrane are improved: reduction of COD rises from 78% to 92 %, concentration polarisation is lower, and therefore the flux increases up to 53 L·h-1·m-2. This value still remains lower than the organic membrane fluxes (respectively 80 L·h-1·m-2 for organic membranes and 25 L·h-1·m-2 for N01A). However, coagulation may not be the appropriate pretreatment because the fouling index of the supernatant after coagulation was similar to that of the raw leachate. Permeability measurements after treatment show that internal fouling is still important (25%). In fact, coagulation does not remove molecules with molecular weights around 500 Daltons, and consequently these particles still obstruct the membrane pores. The phenomenon limits the performance (flux) of this membrane

Graphene Nanogap for Gate Tunable Quantum Coherent Single Molecule Electronics

We present atomistic calculations of quantum coherent electron transport through fulleropyrrolidine terminated molecules bridging a graphene nanogap. We predict that three difficult problems in molecular electronics with single molecules may be solved by utilizing graphene contacts: (1) a back gate modulating the Fermi level in the graphene leads facilitate control of the device conductance in a transistor effect with high on/off current ratio; (2) the size mismatch between leads and molecule is avoided, in contrast to the traditional metal contacts; (3) as a consequence, distinct features in charge flow patterns throughout the device are directly detectable by scanning techniques. We show that moderate graphene edge disorder is unimportant for the transistor function.Comment: 8 pages, 6 figure

Benchmarking van der Waals Density Functionals with Experimental Data: Potential Energy Curves for H2 Molecules on Cu(111), (100), and (110) Surfaces

Detailed physisorption data from experiment for the H_2 molecule on low-index Cu surfaces challenge theory. Recently, density-functional theory (DFT) has been developed to account for nonlocal correlation effects, including van der Waals (dispersion) forces. We show that the functional vdW-DF2 gives a potential-energy curve, potential-well energy levels, and difference in lateral corrugation promisingly close to the results obtained by resonant elastic backscattering-diffraction experiments. The backscattering barrier is found selective for choice of exchange-functional approximation. Further, the DFT-D3 and TS-vdW corrections to traditional DFT formulations are also benchmarked, and deviations are analyzed.Comment: 15 pages, 9 figure

Evaluation of New Density Functional with Account of van der Waals Forces by Use of Experimental H2 Physisorption Data on Cu(111)

Detailed experimental data for physisorption potential-energy curves of H2 on low-indexed faces of Cu challenge theory. Recently, density-functional theory has been developed to also account for nonlocal correlation effects, including van der Waals forces. We show that one functional, denoted vdW-DF2, gives a potential-energy curve promisingly close to the experiment-derived physisorptionenergy curve. The comparison also gives indications for further improvements of the functionals

Shallow impurity band in ZrNiSn

ZrNiSn and related half Heusler compounds are candidate materials for efficient thermoelectric energy conversion with a reported thermoelectric figure-of-merit of n-type ZrNiSn exceeding unity. Progress on p-type materials has been more limited, which has been attributed to the presence of an impurity band, possibly related to the presence of Ni interstitials in nominally vacant 4d position. The specific energetic position of this band, however, has not been resolved. Here, we report results of a concerted theory-experiment investigation for a nominally undoped ZrNiSn, based on measurements of electrical resistivity, Hall coefficient, Seebeck coefficient and Nernst coefficient, measured in a temperature range from 80 to 420 K. The results are analyzed with a semi-analytical model combining a density functional theory (DFT) description for ideal ZrNiSn, with a simple analytical correction for the impurity band. The model provides a good quantitative agreement with experiment, describing all salient features in the full temperature span for the Hall, conductivity, and Seebeck measurements, while also reproducing key trends in the Nernst results. This comparison pinpoints the impurity band edge to 40 meV below the conduction band edge, which agrees well with a separate DFT study of a supercell containing Ni interstitials. Moreover, we corroborate our result with a separate study of ZrNiSn0.9Pb0.1 sample showing similar agreement with an impurity band edge shifted to 32 meV below the conduction band

Understanding adhesion at as-deposited interfaces from ab initio thermodynamics of deposition growth: thin-film alumina on titanium carbide

We investigate the chemical composition and adhesion of chemical vapour deposited thin-film alumina on TiC using and extending a recently proposed nonequilibrium method of ab initio thermodynamics of deposition growth (AIT-DG) [Rohrer J and Hyldgaard P 2010 Phys. Rev. B 82 045415]. A previous study of this system [Rohrer J, Ruberto C and Hyldgaard P 2010 J. Phys.: Condens. Matter 22 015004] found that use of equilibrium thermodynamics leads to predictions of a non-binding TiC/alumina interface, despite the industrial use as a wear-resistant coating. This discrepancy between equilibrium theory and experiment is resolved by the AIT-DG method which predicts interfaces with strong adhesion. The AIT-DG method combines density functional theory calculations, rate-equation modelling of the pressure evolution of the deposition environment and thermochemical data. The AIT-DG method was previously used to predict prevalent terminations of growing or as-deposited surfaces of binary materials. Here we extent the method to predict surface and interface compositions of growing or as-deposited thin films on a substrate and find that inclusion of the nonequilibrium deposition environment has important implications for the nature of buried interfaces.Comment: 8 pages, 6 figures, submitted to J. Phys.: Condens. Matte