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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 10460-10466 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The structure of oxygen adsorbed on Ir{100} has been determined by density functional theory slab calculations and quantitative low energy electron diffraction. The two studies produce essentially identical results, experiment providing a benchmark for the first principles calculation, while the latter provides a more complete understanding of the structure. Oxygen forms a (1×2) overlayer with adsorption on the bridge site: an unusual result for oxygen. There is a significant row pairing of the iridium atoms in the surface layer which strongly stabilizes the structure, and is one of the main factors favoring the bridge site occupation and the (1×2) configuration. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 8631-8636 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: An unusually high-peak-temperature desorption state of O2 from Pt{110} (1×2) has been characterized in temperature programmed desorption spectra after O2 adsorption from a supersonic beam at a translational energy of 190 meV and at nozzle temperatures, Tn, greater than 870 K. It shows the characteristics of a subsurface atomic state of oxygen. From the nozzle temperature dependence of the rate of population of this state we conclude that it is formed exclusively from electronically excited O2 1Δg generated in the molecular beam source. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 12082-12088 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The chemisorption of NO on Pt{110}-(1×1) and -(1×2) has been studied using density functional theory slab calculations with the generalized gradient corrections. On both surface phases the monomeric species is the most stable and the short-bridge sites are energetically the most favorable adsorption sites. Monomeric NO is adsorbed upright with its molecular axis normal, bonded to the surface through the N atom. On the (1×2) surface at high coverage a polymeric (NO)x chain structure is identified; this may well correspond to the structure experimentally observed at high coverage on the (1×2) surface formed after heating a multilayer to temperatures between 80 K and 200 K, characterized by an NO IR band at 1760 cm−1. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 10996-11009 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The kinetics of CO chemisorption on both the (1×5) and (1×1) surfaces of Ir{100}, including the CO-induced surface restructuring process, have been studied by measuring the sticking probability as a function of the surface temperature and beam flux. Due to competition between desorption from the (1×5) phase and growth of (1×1) islands, the sticking probability on the initial (1×5) surface is strongly flux-dependent at surface temperatures Ts in the range 480≤Ts≤510 K. It is shown that this is due to a strongly nonlinear dependence of the (1×1) growth rate on the local CO coverage on the (1×5) substrate, with an apparent reaction order of around 5. Desorption energies and pre-exponentials of desorption for CO from both the (1×1) and (1×5) surfaces have been determined by means of a modified lifetime measurement technique. Equilibrium coverages as well as isothermal desorption rates of CO were determined for both surface phases. The zero coverage desorption energy of CO from the (1×1) substrate is 196±5 kJ/mol and from the (1×5) surface it is around 150 kJ/mol. This difference in adsorption energies is the driving force for the CO-induced (1×5) to (1×1) phase transition. TEAS data show that the local CO coverage on the growing (1×1) islands during the phase transformation is 0.5 ML. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 5609-5612 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Clear evidence for the nonthermal acoustic wave enhancement of a catalytic reaction over a single crystal metal surface under controlled conditions is provided in this Letter. Data demonstrating a fourfold increase in the rate of CO oxidation over a thin Pt{110} catalyst bonded onto the surface of a piezoelectric interdigital transducer is discussed here together with a possible mechanism for this effect. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 1210-1215 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ab initio total energy calculations using density functional theory with the generalized gradient approximation have been performed for the chemisorption of oxygen atoms on a Pt{100}-(1×1) slab. Binding energies for the adsorption of oxygen on different high-symmetry sites are presented. The bridge site is the most stable at a coverage of 0.5 ML, followed by the fourfold hollow site. The atop site is the least stable. This finding is rationalized by analyzing the "local structures" formed upon oxygen chemisorption. The binding energies and heats of adsorption at different oxygen coverages show that pairwise repulsive interactions are considerably stronger between oxygen atoms occupying fourfold sites than those occupying bridge sites. Analysis of the partial charge densities associated with Bloch states demonstrates that the O–Pt bond is considerably more localized at the bridge site. These effects cause a sharp drop in the heats of adsorption for oxygen on hollow sites when the coverage is increased from 0.25 to 0.5 ML. Mixing between oxygen p orbitals and Pt d orbitals can be observed over the whole metal d-band energy range.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 1990-1996 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The coverage dependencies of the differential heats of adsorption for CO and NO on Pd{100}, at room temperature, are reported using single crystal adsorption calorimetry (SCAC). The initial heat for CO is 165 kJ/mol, falling markedly with increasing coverage due to anomalously strong repulsive interactions between molecules. The formation of a c(2×4) overlayer at half monolayer coverage places severe constraints on the magnitudes of lateral interactions between adsorbates which can fit the data. A realistic lateral interaction model is proposed. The influence of predosed carbon on the heat of adsorption of CO was also investigated. As little as 0.05 ML of C causes a decrease in the initial heat of about 20 kJ/mol; 0.2 ML reduces the heat to 120 kJ/mol. The results suggest long range interactions between C atoms and CO molecules. The initial heat for NO is 155 kJ/mol, decreasing smoothly to about 105 kJ/mol at saturation. The coverage dependencies of the sticking probabilities for both NO and CO exhibits precursor behavior which is considerably diminished in the presence of a high C precoverage. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 2012-2030 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using single-crystal adsorption calorimetry, heat data have been measured for the adsorption of oxygen on the three low-index planes of Ni at 300 K along with corresponding sticking probabilities. New data are presented with coadsorbed potassium on each plane, and temperature-dependent data for O2/Ni{100}. The initial heats of adsorption of oxygen on Ni{100}, {110}, and {111} are 550, 475, and 440 kJ (mol O2)−1, respectively, at 300 K, and the heat is found to drop rapidly with coverage in the chemisorption regime, indicating strong interadsorbate interactions. However, this rapid decline is not seen with coadsorbed potassium, a difference discussed both in terms of electron availability and coadsorbate attractions. The integral heats of adsorption for oxide film formation are 220, 290, and 320 kJ mol−1, respectively. Corresponding sticking probability measurements show initial values, all less than unity, of 0.63, 0.78, and just 0.23, again for the {100}, {110}, and {111} surfaces in that order. The coverage dependence of the sticking probability is consistent in each case with a passivating oxide film four layers thick. Comparable data for Ni{100} obtained using a pyroelectric detector gave good agreement with the conventional results at 300 K. At 410 K, however, the heat-coverage curve was flat up to 0.25 monolayers. Data were also obtained at 90 K. Analysis and Monte Carlo simulation of the temperature-dependent adsorption heat curves indicates that the large drop in adsorption heat with coverage seen at room temperature is consistent with a local second-nearest neighbor adatom–adatom repulsion rather than a long-range electronic effect. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 16002-16010 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 1937-1945 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The C oxidation reaction on Pt{110}(1×2) has been investigated using molecular beam techniques. The reaction products are CO and CO2. As the surface temperature is increased from 550 to 750 K, the proportion of CO2 produced decreases from ∼50% to 〈1%. When oxygen first impinges on the surface, the formation rate of CO is observed to rise immediately (≤0.1 s), and then rise more slowly to a maximum before decreasing sharply as the C adlayer is depleted. The production of CO2 is initiated after a measurable delay. Angle-resolved product distribution measurements demonstrate that CO desorbs in a sharp lobe centered at an angle of 32° to the surface normal, fitted to cosn(θ−32), where n=50±5. The C oxidation reaction site is identified with the (111) microfacets. It is concluded that two processes are operative, a Langmuir–Hinshelwood mechanism and a reaction in which CO is impulsively desorbed. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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