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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 93 (1990), S. 5327-5336 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ultraviolet-photochemistry of molecularly adsorbed oxygen on Pd(111) has been studied using pulsed laser light with 6.4 eV photon energy. Three processes occur upon irradiation: desorption of molecular oxygen, conversion between adsorption states, and dissociation to form adsorbed atomic oxygen. By using time-of-flight spectroscopy to detect the desorbing molecular oxygen and post-irradiation thermal desorption spectroscopy (TDS) to characterize the adsorbate state, a detailed picture of the photochemical processes is obtained. The data indicate that the O2 molecules desorbing with low translational energies from the saturated surface as well as the conversion of adsorbed molecules between binding states are induced by the photoinduced build-up of atomic oxygen on the surface. Analysis of a proposed reaction model reproduces the observed data and yields detailed rates. Polarization analysis indicates that the photochemical processes are initiated by electronic excitations of the substrate.
    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 92 (1990), S. 3154-3169 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ultraviolet irradiation of NO2 adsorbed on top of a NO saturated Pd(111) surface causes the photodissociation of NO2/N2O4 and results in the desorption of NO molecules. This process has been studied using excitation energies between 3.5 and 6.4 eV. At a photon energy of 6.4 eV, a cross section of 3×10−18 cm2 is found. Using laser-induced fluorescence to detect the desorbed NO molecules, fully state-resolved data detailing the energy channeling into different degrees of freedom has been obtained. Two desorption channels are found, one characterized by nonthermal state populations, and one showing accommodation to the surface. The yield of the fast channel shows a marked increase above 4 eV photon energy. The slow channel is interpreted as being due to NO molecules which, after formation, undergo a trapping–desorption process. A polarization experiment indicates that the photodissociation is initiated by excitation of metal electrons rather than direct absorption by the adsorbate.
    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 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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  • 5
    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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  • 6
    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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  • 7
    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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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 4609-4619 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: UV-laser irradiation (hν=6.4 eV and 5.0 eV) of the water bilayer adsorbed on a Pd(111) surface leads to molecular desorption and to conversion of the adsorbed state as manifested in thermal desorption spectra. The latter effect is attributed to photodissociation of water on the surface. Time-of-flight measurements show that water molecules desorb with a translational energy of about 600 K for both photon energies indicating a nonthermal process. While desorption is largely suppressed with adsorbed multilayers, conversion within the first layer still proceeds. The dependence of the desorption yield on angle of incidence and polarization of the light reveals substrate excitations as the dominant primary step. A strong variation of cross sections with isotopic substitution is observed. This is interpreted as evidence for the operation of a mechanism involving excitation onto an isotope-independent excited potential energy surface followed by rapid deexcitation to the ground state so that, of the total number of species excited, only a small mass dependent fraction actually fragments or desorbs.
    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 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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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 1509-1510 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ultraviolet-laser irradiation (6.4 eV and 5.0 eV) of the first layer of water adsorbed on a Pd(111) surface at 90 K leads to desorption of H2O and to conversion of the adsorbed state as manifested in the thermal desorption spectra. The latter effect is attributed to photodissociation of water on the surface. Time-of-flight measurements show that water molecules desorb with the same translational energy of about 600 K for both photon energies. While desorption is suppressed with adsorbed multilayers, conversion within the first layer still proceeds.
    Type of Medium: Electronic Resource
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