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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3696-3704 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High translational energy adsorption of oxygen on the (111) surface of platinum was examined with electron energy loss spectroscopy (EELS) and molecular beam techniques. EEL spectra indicate that over an incident energy range of 0.2–1.37 eV and on a Pt(111) surface held at 77 K, oxygen adsorbs in an associative chemisorbed state—yielding to the dissociated state only after sufficient substrate heating. Simple direct dissociation appears negligible for all incident kinetic energies studied. At near-zero surface coverages, exclusive population of the peroxolike molecular precursor is observed for adsorption at these high translational energies, while both superoxolike and peroxolike forms are detected for low energy adsorption (0.055 eV). This peculiarity represents evidence that translational energy is effective in differentially populating reaction intermediates and provides better quantification of potential energy barriers to dissociation. We estimate the activation barrier for dissociation from the peroxolike precursor to be approximately 0.29 eV. Initial adsorption probability measurements over a wide range of surface temperatures and high incident kinetic energies corroborate a molecular chemisorption mediated mechanism. © 1999 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 105 (1996), S. 8362-8375 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The interaction of nitric oxide (NO) with an Ir(111) surface has been studied with supersonic molecular beam techniques and electron energy loss spectroscopy. Initial adsorption probability S0, measurements as a function of incident kinetic energy Ei, surface temperature Ts, and angle of incidence θi reveal that separate mechanisms govern adsorption at low and high kinetic energy. This distinction is reflected in measurements of the initial molecular adsorption probability where a decrease in the value of S0 with increasing Ts (between 77 and 300 K) is observed at low kinetic energy (Ei〈0.45 eV), but no surface temperature dependence is detected at high kinetic energy in this temperature range. We present a model describing both the molecular and dissociative chemisorption of NO on Ir(111). At low kinetic energy, NO adsorbs initially as a physically adsorbed species. From this state, desorption to the gas phase or conversion to a molecularly chemisorbed state on the surface are competing processes which depend on surface temperature. The molecularly chemisorbed state is the precursor to dissociation for elevated surface temperatures. At high kinetic energy, NO adsorption occurs directly into the molecularly chemisorbed well, with the probability of trapping as a physically adsorbed species near zero and with undetectable direct dissociation. Indeed, after exposure of the Ir(111) surface at 77 K to a high kinetic energy (1.3 eV) beam, surface vibrational spectroscopy measurements show only features attributable to molecularly chemisorbed NO. The success of this model in describing our measurements is demonstrated by the separate calculation from low and high kinetic energy data of rate constants corresponding to forward and reverse conversion from the molecularly chemisorbed well. Additionally, we discuss attempts to promote dissociation on the surface with vibrational energy and with a combination of translational and surface thermal energy. © 1996 American Institute of Physics.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 943-952 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The initial dissociative chemisorption probability, S0, of O2 on Ir(111) has been investigated with molecular beam techniques and electron energy loss spectroscopy (EELS). The adsorption process on the clean surface occurs by distinct dynamical mechanisms. At incident kinetic energies, Ei, of 0.1 eV and below, the dissociative chemisorption probability decreases with increasing kinetic energy, indicating the dominance of a trapping-mediated mechanism. A decrease in the value of S0 with increasing surface temperature, Ts, is also characteristic of this regime. This temperature dependence reflects the participation of a physically adsorbed state and molecularly chemisorbed state in the dissociation scheme. Additionally, the dependence of S0 on incident angle, θi, in the low kinetic energy regime exhibits near normal energy scaling. At high kinetic energy (Ei〉0.1 eV), the initial dissociative chemisorption probability rises with increasing Ei indicating that translational energy is effective in surmounting a potential barrier to adsorption. Direct access of a molecularly chemisorbed state followed by dissociation, rather than direct access of the dissociated state, is hypothesized to be the primary initial adsorption step. Several observations support this mechanism, including a temperature dependence in the high kinetic energy regime and no observed increase in oxygen saturation coverage with increasing kinetic energy. In addition, EEL spectra show that molecularly chemisorbed states of oxygen are formed on the Ir(111) surface at Ts〈70 K after exposure to a 1.36 eV beam and partial saturation of the atomic overlayer. Attempts to identify molecularly chemisorbed oxygen at low coverages were unsuccessful and limited by the experimental setup which provides cooling of the iridium crystal to only ∼68 K. © 1997 American Institute of Physics.
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