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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Langmuir 3 (1987), S. 4-12 
    ISSN: 1520-5827
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    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 91 (1989), S. 4942-4948 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rate of catalytic carbon monoxide oxidation on a Pt(100) single crystal surface under isothermal, low-pressure conditions exhibits for certain ranges of parameters (O2 and CO partial pressures, temperature) sustained temporal oscillations whose mechanism had been explored in previous work. Coupling between reaction and diffusion leads to spatial pattern formation as manifested by patches with different work function on the intrinsically homogeneous surface. Imaging is performed by means of the novel technique of scanning photoemission microscopy. Typically, nuclei with dimensions of a few microns, as determined by the instrumental resolution, are formed spontaneously and expand with sharp fronts and velocities of about 0.5 mm/min (at 480 K) up to sizes ≥1 mm. Waves with even more extended fronts propagating with somewhat higher velocities across the sample surface are responsible for the occurrence of large amplitude temporal oscillations of the integral reaction rate.
    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 91 (1989), S. 5002-5010 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: If a Pt(100) sample is kept at steady-state conditions of O2 and CO partial pressures and temperature which are similar to those for the occurrence of autonomous temporal oscillations in the rate of CO2 formation, then the surface will be largely covered by adsorbed CO which inhibits oxygen adsorption and keeps the catalytic rate low. Irradiation of a small spot with a high power laser pulse causes momentarily local thermal desorption of CO and creation of a reaction front which propagates as a chemical wave across the surface area, as was monitored by the excursion of the integral reaction rate and locally by means of a work function (=oxygen coverage) probe placed at several mm distance from the spot of irradiation. The velocity for wave propagation rises from about 2 mm/min at 480 K to 4 mm/min at 507 K and is not noticeably dependent on the partial pressures. The mechanism is closely related to that for self-sustained kinetic oscillations of this system and exhibits the typical features of trigger waves: Coupling between autocatalytic reaction and diffusion, as well as the occurrence of a refractory period during which the system is "dead,'' and of a threshold for the intensity of the excitation.
    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 87 (1987), S. 6191-6198 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: From an analysis of the low-energy electron diffraction (LEED) intensities we have determined the oscillatory distortion of the topmost interlayer spacings of the clean and the (2×1)H covered Pd(110) surface as well as the exact adsorption geometry in this latter structure, which is formed at T〈180 K at a coverage of θH≤1.0. An R-factor analysis was used for quantitative comparison with the experimental data. The oscillatory distortion of the clean surface— d12=−5.1±1.5%, d23=+2.9±1.5%, d34 at its bulk value of 1.37 A(ring) (with R factors RP=0.22 , RZJ=0.14 )— is found to be reduced by the H adlayer to d12=−2.2±1.5%, d23=+2.9±1.5%, and d34=bulk value. The H atoms are adsorbed on quasi-threefold sites with equal distances of 2.0±0.1 A(ring) to the two nearest Pd neighbors in the topmost and the closest Pd atom in the second layer, leading to an effective radius of the H atom of rH=0.6±0.1 A(ring). The long-bridge adsorption site, (octahedral) subsurface sites, or a hydrogen induced reconstruction via a lateral displacement of topmost Pd atoms by more than ±0.1 A(ring) can clearly be ruled out. These structural data, which are in good agreement with those of ordered Had structures on Ni(110) and Fe(110), characterize the (2×1)H structure on Pd(110) as being a typical adsorbate structure. There is no indication of either direct occupation of distinct subsurface or of near surface adsorption sites in this structure, nor does it open up channels for surface penetration, e.g., by a strong distortion of the topmost Pd substrate layers. In contrast to Ni(110) and Rh(110) the island growth of the (2×1)H structure on Pd(110) indicates predominantly attractive, indirect adatom–adatom interaction which, however, are of distinctly different nature than those causing island formation in the Pd–hydride phase.
    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 87 (1987), S. 742-749 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Periodic modulations of oxygen pressure or temperature were applied in the catalytic oxidation of CO on a Pt(100) surface under isothermal, low pressure conditions. Transitions from aperiodic autonomous oscillations to regular phase-locked behavior could be observed. Computer simulations using a stochastic cellular automaton model yielded qualitatively similar results. The spatial distribution in both experiment and simulation varies essentially in phase over the whole surface area under the influence of the periodic perturbation, while wave propagation in the autonomous system causes more irregular overall behavior.
    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 85 (1986), S. 5328-5336 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The previously observed phenomena of temporal and spatial self-organization during the catalytic oxidation of CO on a Pt(100) surface were computer simulated by use of the cellular automaton technique. The underlying model is footed on the knowledge about the individual reaction steps (adsorption, desorption, surface structural transformation, etc.), which in turn formed the basis of a previous theoretical treatment in terms of the formulation and solution of a set of coupled differential equations. The present result nicely show the formation and propagation of two-dimensional patterns, and they reproduce qualitatively well all the experimental observations. The development of macroscopic patterns even with an a priori perfectly homogeneous surface is a particularly interesting effect.
    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 86 (1987), S. 2411-2422 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ultraviolet photoelectron spectroscopy (UPS) and electron spectroscopy by deexcitation of metastable noble gas atoms (MDS) were used to follow the continuous oxidation of Cs films. While UPS has a finite information depth, MDS probes only the properties of the outermost atomic layer. Small doses of O2 cause the formation of a "monolayer'' of Cs11O3 in which the O2− ions are incorporated below the surface, while the surface itself consists merely of metallic Cs atoms. Further uptake of oxygen leads to a continuous transformation of the subsurface layer into Cs2O2, while a small concentration of adsorbed O atoms builds up on the surface which act as nucleation centers for subsurface oxidation. Finally, the surface layer is completely oxidized into CsO2 which then retards further oxygen penetration into the bulk. The chemical state of the surface can be directly correlated with the associated change of the work function. A monolayer of Cs adsorbed on a Cu(110) surface exhibits quite different properties.
    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 90 (1989), S. 510-521 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rate of catalytic CO oxidation on Pt(100) and (110) surfaces at low pressures (≤10−4 Torr) and under isothermal conditions may exhibit sustained temporal oscillations which are coupled with periodic transformations of the surface structures between reconstructed and nonreconstructed phases, the latter exhibiting higher oxygen sticking coefficients and hence higher reactivity. With Pt(100) the two surface phases exhibit a much larger difference in reactivity (=oxygen sticking coefficient) than with Pt(110), which effect accounts for the qualitative differences in the oscillatory behavior: if two of the control parameters (say pO2, T) are kept fixed, the third (pCO) may be varied with Pt(100) over a fairly wide range without leaving the oscillatory region. Minor (〈1%) fluctuations of the partial pressures associated with the varying reaction rate are hence without any noticeable effect. Coupling between surface reaction and diffusion causes wave propagation of the surface phase transformations and therefore spatial self-organization, as demonstrated by scanning LEED experiments. With Pt(110), on the other hand, the oscillatory region is very narrow. In this case mass transport through the gas phase as caused by the small pressure variations associated with the reaction lead to synchronization between different parts of the surface. Computer simulations with the cellular automaton technique confirm qualitatively the experimental findings and support the conclusions reached.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 83 (1985), S. 1959-1968 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: From an analysis of the low-energy electron diffraction (LEED) intensities we have determined the adsorption geometry of the two ordered H adlayers formed at T〈270 K on Fe (110): a (2×1) and a (3×1) structure, with ideal coverages of θ= 1/2 and θ= (2)/(3) . Calculations were performed for different adsorption sites and structural models, taking the Fe–H bond length and the first Fe–Fe interlayer spacing as variable parameters. An R factor analysis was used for quantitative comparison with the experimental data. In both structures the H atoms are adsorbed on highly coordinated (i.e., quasithreefold) sites: The R factors of only the superlattice beams (RZanazzi–Jona=0.26, RPendry=0.55 in the (2×1) and RZJ=0.4, RP=0.58 in the (3×1) structure) are significantly lower than those from models with a long bridge adsorption site (RZJ=0.37, RP=0.66 and RZJ=0.6, RP=0.74). The on top site and the short bridge site can clearly be ruled out. For both structures the minima occur at the same Fe–H interlayer spacing of 0.9±0.1 A(ring), equivalent to an Fe–H distance of 1.75±0.05 A(ring) or rH=0.47±0.05 A(ring). From the R factor minimum of all beams(RZJ=0.23, RP=0.46) the first Fe–Fe interlayer spacing is found to be equal to its bulk value, like on the clean surface. In the (2×1) structure the only possible arrangement of the Had atoms consists of dense packed rows in [001] direction which are separated by a row of unoccupied sites, respectively, due to a delocalization of the H atoms over two neighboring threefold sites, short-range fluctuations can be envisaged. Their influence upon I/V curves and relative intensities of different superlattice beams was analyzed. As a result this effect could be excluded, large domains are required, in which only one type of threefold sites is occupied. For the (3×1) structure a model is favored in which the lateral distribution of the adatoms differs from a previous suggestion. It is shown that this model is more plausible in view of the H–H interactions. The higher density of threefold sites also has implications for the discussion of the 2D phase diagram of H/Fe (110), especially on the requirement of trio interactions.
    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 83 (1985), S. 1578-1587 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Experimental investigations on the catalytic oxidation of CO on well-defined Pt(100) surfaces at low pressures (∼10−4 Torr) revealed under certain conditions the occurrence of kinetic oscillations which were associated with periodic transformations of the surface structure propagating wave-like across the surface area. Based on experimental information about the various elementary steps involved (adsorption, desorption, surface reaction, adsorbate-induced surface structural transformation) a set of coupled differential equations describing the kinetics of the various processes was established. A simplified version of these equations allows analytical treatment and provides qualitative insight into the occurrence of oscillations through linear stability analysis. Numerical solution of the full set of reaction-diffusion equations reproduces the essential spatio-temporal features of the experimental observations, although full quantitative agreement would still require better adjustment of the parameters involved as well as further refinement of the model.
    Type of Medium: Electronic Resource
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