A density functional theory study of CO and atomic oxygen chemisorption on Pt(111)

Ab initio total energy calculations within a density functional theory framework have been performed for CO and atomic oxygen chemisorbed on the Pt(111) surface. Optimised geometries and chemisorption energies for CO and O on four high-symmetry sites, namely the top, bridge, fee hollow and hcp hollow sites, are presented, the coverage in all cases being 0.25 ML. The differences in CO adsorption energies between these sites are found to be small, suggesting that the potential energy surface for CO diffusion across Pt(111) is relatively flat. The 5 sigma and 2 pi molecular orbitals of CO are found to contribute to bonding with the metal. Some mixing of the 4 sigma and 1 pi molecular orbitals with metal states is also observed. For atomic oxygen, the most stable adsorption site is found to be the fee hollow site, followed in decreasing order of stability by the hcp hollow and bridge sites, with the top site being the least stable. The differences in chemisorption energies between sites for oxygen are larger than in the case of CO, suggesting a higher barrier to diffusion for atomic oxygen. The co-adsorption of CO and O has also been investigated. Calculated chemisorption energies for CO on an O/fcc-precovered surface show that of the available chemisorption sites, the top site at the oxygen atom's next-nearest neighbour surface metal atom is the most stable, with the other four sites calculated bring at least 0.29 eV less stable. The trend of CO site stability in the coadsorption system is explained in terms of a 'bonding competition' model. (C) 2000 Elsevier Science B.V. All rights reserved.

A density functional theory study of CH2 and H adsorption on Ni(111)

Ab initio total energy calculations within the density functional theory framework have been used to study the adsorption of CH2 and H as well as the coadsorption of CH2 and H on Ni(111). H binds strongly at threefold hollow sites with calculated adsorption energies of 2.60 and 2.54 eV at the face-centered-cubic (fcc) and hexagonal-close-packed (hcp) hollow sites, respectively. Adsorption energies and H-Ni distances are found to agree well with both experimental and theoretical results. CH2 adsorbs strongly at all high symmetry sites with calculated adsorption energies of 3.26, 3.22, 3.14 and 2.36 eV at the fcc, hcp, bridge and top sites, respectively. Optimized structures are reported at all sites, and, in the most stable hollow sites there is considerable internal reorganization of the CH2 fragment. The CH2 molecule is tilted, the hydrogens are inequivalent and the C-H bonds are lengthened relative to the gas phase. In the CH2-H coadsorption systems the adsorbates have a tendency to move toward bridge sites. The bonding of all adsorbates to the surface is analyzed in detail. (C) 2000 American Institute of Physics. [S0021-9606(00)71213-X].

A density functional theory study on the interaction between chemisorbed CO and S on Rh(111)

Density functional theory calculations are carried out for Rh(111)-p(2 x 2)-CO, Rh(111)-p(2 x 2)-S, Rh(111)-p(2 x 2)-(S + CO), Rh(111)-p(3 x 3)-CO, Rh(111)-p(3 x 3)-S and Rh(111)-p(3 x 3)-(S + CO), aiming to shed some light on the S poisoning effect. Geometrical structures of these systems are optimized and chemisorption energies are determined. The presence of S does not significantly influence the geometrical structure and chemisorption energy of CO and vice versa, which strongly suggests that the interaction between CO and S on the Rh(111) surface is mainly short-range in nature. The long range electronic effect for the dramatic attenuation of the CO methanation activity by sulfur is likely to be incorrect. It is suggested that an ensemble effect may be dominant in the catalytic deactivation. (C) 1999 Elsevier Science B.V. All rights reserved.

ALBUM AMICORUM de Jean Durand (1583-1592). In-8 de 2 f. lim. et 380 p., mar. r., comp. de mos. de mar. v., riche dorure à petits fers, tr. dor. et ciselée. (Rel. du XVIe siècle.)

Durand (Jean). Album amicorum (1583-1592)

Photoschaltbare Azobenzol-modifizierte selbstorganisierte Monoschichten auf Gold(111)-Oberflächen

Für die Entwicklung photoschaltbarer selbstorganisierter Monoschichten (SAMs) auf Gold(111)-Oberflächen wurden neue Azobenzol-terminierte Asparagussäure - und Liponsäurederivate synthetisiert. Um den Einfluss lateraler Wasserstoffbrückenbindungen auf Qualität und Orientierungsordnung der Schichten zu untersuchen, wurden Monolagen, die durch amid- und esterverknüpfte Verbindungen gebildet wurden, miteinander verglichen. Die Filmbildung aus der Lösung wurde in situ durch optische Frequenzverdopplung (SHG) untersucht und die Photoreaktivität mittels Kontaktwinkelmessungen, Oberflächen-Plasmonenresonanz (SPR) und Ellipsometrie verfolgt. SAMs auf Gold wurden außerdem mit Hilfe von Röntgenphotoelektronenspektroskopie (XPS), Nahkanten-Reflexions-Röntgenabsorptionsspektroskopie (NEXAFS) und Infrarot-Reflexionsabsorptionsspektroskopie (IRRAS) charakterisiert, um die Filmqualität, die Bindung ans Substrat und Orientierungsordnung im Film zu ermitteln. Da die Chemisorption auf polykristallinem Gold formal der Koordinationschemie von 1,2-Dithiolan-Derivaten gegenüber nullwertigen Edelmetall-Zentralatomen entspricht, wurden etliche Pt-Komplexe durch oxidative Addition an [Pt(PPh3)4] dargestellt. Im Zusammenhang mit der Darstellung der Asparagussäure wurde die Kristallstruktur von [pipH]2[WS4] und der neuen Verbindungen [pipH]3[WS4](HS) und [pipH]4[WS4][WOS3] (pip = Piperidin) bestimmt. Wasserstoffbrückenbindungen zwischen den Piperidinium-Kationen und den Thiowolframat-Anionen spielen eine dominante strukturelle Rolle.

Quadrupole moments of radium isotopes from the 7p^2P_3/2 hyperfine structure in Ra II

The hyperfine structure and isotope shift of ^{221- 226}Ra and ^{212, 214}Ra have been measured in the ionic (Ra 11) transition 7s^2 S_{1/2} - 7p ^2 P_{3/2} (\lamda = 381.4 nm). The method of on-line collinear fast-beam laser spectroscopy has been applied using frequency-doubling of cw dye laser radiation in an external ring cavity. The magnetic hyperfine fields are compared with semi-empirical and ab initio calculations. The analysis of the quadrupole splitting by the same method yields the following, improved values of spectroscopic quadrupole moments: Q_s(^221 Ra)= 1.978(7)b, Q_s (^223 Ra)= 1.254(3)b and the reanalyzed values Q_s(^209 Ra) = 0.40(2)b, Q_s(^211 Ra) = 0.48(2)b, Q_s(^227 Ra)= 1.58(3)b, Q_s (^229 Ra) = 3.09(4)b with an additional scaling uncertainty of ±5%. Furthermore, the J-dependence of the isotope shift is analyzed in both Ra II transitions connecting the 7s^2 S_{1/2} ground state with the first excited doublet 7p^ P_{1/2} and 7p^ P_{3/2}.

Proyecto cambio 2 : un programa de educación ambiental para las ciencias.

Resumen tomado de la publicación

Formación del profesorado y Tecnologías de la Información y la Comunicación : renovación y convergencia para la educación 2.0 en el '(ciber) Espacio Europeo de Educación Superior'.

Monográfico con el título: 'Convergencia tecnológica: la producción de pedagogías high tech'. Resumen basado en el de la publicación

Herramientas 2.0 al servicio del e-learning colaborativo.

Resumen basado en el de la publicación

La educación en las revistas : 1960, 2ª quincena febrero.

Reseña de artículos sobre temas educativos y afines publicados en revistas y diarios españoles en 1960 y que se agrupan en los siguientes epígrafes: Enseñanza primaria; Enseñanza media y Enseñanza universitaria. Estas publicaciones son: 'Revista Calasancia de Educación'; 'Revista Española de Pedagogía'; 'Familia Española', 'Vida Escolar'; 'Cuadernos de Orientación', 'Revista Española de Filosofía'; y el periódico 'Arriba'.

The surface structure of BaO on Pt(111): (2x2)-reconstructed BaO(111)

The surface structure of BaO(111) has been determined using STM and computer modelling. The BaO(111) surface was prepared in thin film form on Pt(111) and presents a surface with twice the lattice parameter expected for that of the bulk termination, i.e. a (2 x 2) reconstruction. Computer modelling indicates that the bulk termination is unstable, but that the (2 x 2) reconstructed BaO(111) surface has a low surface energy and is hence a stable surface reconstruction. The (2 x 2) reconstruction consists of small, three-sided pyramids with (100) oriented sides and either oxygen or barium ions at the apices. Less regular surface reconstructions containing the same pyramids are almost equally stable, indicating that we may also expect less regular regions to appear with a fairly random distribution of these surface species. The simulations further suggest that a regular (4 x 4) reconstruction built up of bigger pyramids is even more energetically favourable, and some evidence is found for such a structure in the STM. (c) 2006 Elsevier B.V. All rights reserved.

Bis[1,1 '-N,N '-(2-picolyl)aminomethyl]ferrocene as a redox sensor for transition metal ions

The compound bis[1,1'-N,N'-(2-picolyl) aminomethyl] ferrocene, L-1, was synthesized. The protonation constants of this ligand and the stability constants of its complexes with Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ were determined in aqueous solution by potentiometric methods at 25degreesC and at ionic strength 0.10 mol dm(-3) in KNO3. The compound L-1 forms only 1:1 (M:L) complexes with Pb2+ and Cd2+ while with Ni2+ and Cu2+ species of 2:1 ratio were also found. The complexing behaviour of L-1 is regulated by the constraint imposed by the ferrocene in its backbone, leading to lower values of stability constants for complexes of the divalent first row transition metals when compared with related ligands. However, the differences in stability are smaller for the larger metal ions. The structure of the copper complex with L-1 was determined by single-crystal X-ray diffraction and shows that a species of 2:2 ratio is formed. The two copper centres display distorted octahedral geometries and are linked through the two L1 bridges at a long distance of 8.781(10) Angstrom. The electrochemical behaviour of L-1 was studied in the presence of Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+, showing that upon complexation the ferrocene-ferrocenium half-wave potential shifts anodically in relation to that of the free ligand. The maximum electrochemical shift (DeltaE(1/2)) of 268 mV was found in the presence of Pb2+, followed by Cu2+ (218 mV), Ni2+ (152 mV), Zn2+ (111 mV) and Cd2+ (110 mV). Moreover, L-1 is able to electrochemically and selectively sense Cu2+ in the presence of a large excess of the other transition metal cations studied.

6,6 '-bis-(5,6-diethyl-[1,2,4]triazin-3-yl)-2,2 '-bipyridyl the first example of a new class of quadridentate hetercyclic extraction reagents for the separation of americium(III) and europium(III)

The synthesis of the first example of a new class of tetradentate reagents for the efficient separation of americium(Ill) and europium(111) is reported together with the structure of the complex formed with europium(III), (C) 2004 Elsevier B.V. All rights reserved.

Chemical composition and reactivity of water on clean and oxygen-covered Pd{111}

The chemical composition and dissociation behaviour of water adsorbed on clean and oxygen pre-covered Pd{111} was studied using high-resolution time-resolved and temperature-programmed X-ray photoelectron spectroscopy. We find that water remains intact at all temperatures up to desorption on the clean surface and at high oxygen coverage(0.69 ML) when a surface oxide is formed. The highest desorption peaks occur at 163 K from the clean surface and at 172 K from the surface oxide. At the intermediate coverage of 0.20 ML oxygen reacts with coadsorbed water at 155 K, to generate a mixed H2O/OH layer exhibiting a (root 3- x root 3)R30 degrees diffraction pattern, which is stable up to 177 K. The measured ratio between intact water and the hydroxyl species in this layer varies between 1.5 and 2 depending on temperature. (C) 2008 Elsevier B.V. All rights reserved.