Search results for "Faces"
showing 10 items of 3167 documents
Role of the central gold atom in ligand-protected biicosahedral Au 24 and Au25 clusters
2013
The crystal structures of the ligand-protected clusters [Au24(PPh3)10(SC2H4Ph)5Cl2]+ and [Au25(PPh3)10(SC2H4Ph)5Cl2]2+ have been elucidated recently, and they comprise the same biicosahedral structural motif for the Au core. The only difference is the central Au atom joining two icosahedra which is absent in the Au24 cluster. On the basis of density functional simulations, we have evaluated the structural, electronic, optical, and vibrational properties of the clusters in question with a full presentation for the thiolate and phosphine side groups. Our spherical harmonics analysis of the electronic structure shows that the chemical stability of both clusters can be understood based on an 8 …
Adsorption of 3d Transition Elements on a TiO2(110) Surface.
2008
International audience; A first-principles study on the adsorption of 3d transition metal atoms on a stoichiometric TiO2(110) surface is reported. For all 3d elements except Cu, the most stable on-surface adsorption site is a site where the adatom binds to two twofold and one threefold surface oxygen atoms. For Ti, V, and Cr, however, a subsurface site, where the adatom substitutes a sixfold Ti atom, is more stable. The adatoms are oxidized in all cases. The charge transfer to the substrate is larger for the substitutional site than for the on-surface adsorption sites and decreases with atomic number along the 3d series. The relative stabilities of the adsorption sites are discussed in term…
First principles slab calculations of the regular Cu/MgO(001) interface
2004
Ab initio slab calculations are performed for the copper adhesion over magnesium ions on the perfect MgO(0 0 1) surface with 1/4 monolayer (ML), two types of 1/2 ML and 1 ML substrate coverages. Results of our calculations are compared with various experimental and theoretical data. Both small atomic polarization and charge redistribution give the dominant contributions to the physisorption bonding on a regular Cu/MgO(0 0 1) interface.
Intrinsic Metal Size Effect on Adsorption of Organic Molecules on Platinum
2008
Di-σ adsorbed ethene, bridge(30) adsorbed benzene (with four di-σ-type and two π-type interactions), and η1 and η2 adsorbed acetone on nanosized platinum clusters consisting of 19 to 38 Pt atoms were studied theoretically by density functional theory (DFT) calculations with general gradient approximation (GGA) utilizing plane wave and local basis sets. The cluster results were compared to plane wave calculations employed with periodic boundary conditions. It was found that the geometries obtained with different methods are very similar but the adsorption energy depends prominently on the cluster size. Adsorption was strongest on the 22- and 26-atom clusters and weakest on the 35- and 38-ato…
Density Functional Theory Study on Propane and Propene Adsorption on Pt(111) and PtSn Alloy Surfaces
2011
Density functional theory calculations were performed to investigate the adsorption of propane, propene, and C and H atoms on Pt and PtSn surfaces employing the revised Perdew–Burke–Ernzerhof (RPBE) and vdW-DF functionals. Propane adsorption was found to be mediated by van der Waals interactions without significant site preference on any of the studied surfaces. The adsorption characteristics of propene are different: On the Pt(111) and Pt3Sn(111) surfaces, propene adsorption is covalent, and the molecule prefers a di-σ site to a π site. Alloying Pt(111) with Sn leads to weaker adsorption owing to geometric and relaxation effects, whereas electronic effects are found to be small. On the PtS…
Solvent-Independent Electrode Potentials of Solids Undergoing Insertion Electrochemical Reactions: Part I. Theory
2012
A formally solvent-independent redox system can be theoretically defined using the Lovric and Scholz modeling of the voltammetry of microparticles for ion-insertion solids. The proposed theory is based on the extra-thermodynamic assumptions that no net charge accumulates at the solid|electrolyte interface and the assumption that the structure of the solid and the ion binding remain unaffected by the solvent. Under voltammetric conditions, the corresponding redox potential can be estimated from voltammetric and chronoamperometric data assuming electrochemical reversibility and diffusive charge transport in the solution and solid phases, also taking into account ion partition (electrolyte/sol…
Electrosynthesis of Poly(alanine)-Like Peptides in Concentrated Alanine Based Electrolytes, Characterization Coupled to DFT Study and Application to …
2014
The anodic oxidation of concentrated l-alanine on smooth electrodes such as platinum and glassy carbon electrodes was studied. Contrary to the previous studies performed up to now with diluted l-alanine, the electrochemical process generated here results in a completely different situation. The oxidation on smooth platinum was carried out by electrochemical quartz crystal microbalance (EQCM) coupled to cyclic voltammetry technique. The effects of concentration, scan rate, and pH (zwitterion at pH = 6 and alkaline media at pH = 13) on potential values were examined. Glassy carbon and smooth gold electrodes showed the same behavior as on smooth platinum electrode. Spectroscopic analysis such …
Evaluation of the Stability of Pure Silica MCM-41 toward Water Vapor
1999
Water vapor adsorption/desorption isotherms at 298 K and XRD measurements and nitrogen isotherms at 77 K before and after exposure to water vapor were determined on pure silica MCM-41 samples; samples had different pore widths and were prepared by different synthesis methods, including hydrothermal and room-temperature procedures. It was found that prolonged exposure to water vapor provoked structural alterations in all of the MCM-41 materials studied, the most significant effects being a loss of pore shape uniformity and a large decrease in pore size and, in consequence, pore volume. Analysis of the results suggests that these alterations are due to expansion of the pore walls as well as, …
Investigations of TiO2 films deposited by different techniques
1991
High refractive TiO2 films deposited by reactive electron beam evaporation, reactive ion plating and dip coating have been characterized by optical spectroscopy, electron spectroscopy for chemical analysis, Rutherford backscattering spectroscopy, nuclear reaction analysis and Raman spectroscopy. The spectral refractive index n exhibits a strong dependence on the deposition conditions. These findings will be connected to variations in density, stoichiometry, hydrogen content (H2O) and binding structure of the layers. A strong correlation is found between optical quantities and microscopic properties of TiO2 films.
Photoinduced ultrafast dynamics of Ru(dcbpy)2(NCS)2-sensitized nanocrystalline TiO2 films:The influence of sample preparation and experimental condit…
2004
In most of the previous ultrafast electron injection studies of Ru(dcbpy)2(NCS)2-sensitized nanocrystalline TiO2 films, experimental conditions and sample preparation have been different from study to study and no studies of how the differences affect the observed dynamics have been reported. In the present paper, we have investigated the influence of such modifications. Pump photon density, environment of the sensitized film (solvent and air), and parameters of the film preparation (crystallinity and quality of the film) were varied in a systematic way and the obtained dynamics were compared to that of a well-defined reference sample: Ru(dcbpy)2(NCS)2−TiO2 in acetonitrile. In some cases, …