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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 2929-2939 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: State-resolved detection techniques have been used to characterize the ultraviolet photodecomposition dynamics of Mo(CO)6 on Si(111) 7×7 at 100 K. Details of the excitation/fragmentation mechanism including adsorbate energy transfer were examined by measuring the cross sections and the internal and translational energies of the photoejected CO from submonolayer through multilayer coverage regimes. The CO energy distributions are found to be independent of Mo(CO)6 coverage, and can be characterized by two components with markedly different mean energies. In contrast to the coverage independence of the measured energy disposal, the cross section was found to decrease by a factor of 3 from multilayer coverages to submonolayer coverages.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 86 (1999), S. 2785-2789 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: We demonstrate a method of acquiring near-field scanning optical microscopy data that allow for the construction of three different types of images from one data set: topographic, constantgap, and constant-height. This data set includes the topographic features of the surface and the optical response at various heights above the sample surface. Comparisons are made between the images recorded in this format and both conventional, constant-gap mode images, and pseudoconstant-height mode images constructed using a single retraction curve. Zmotion artifacts are identified by analyzing the optical intensity for a given image as a function of the sample topography. Using this procedure it is shown that significant z-motion artifacts exist in the constant-gap images of gold particles immobilized on a glass slide. These artifacts are avoided by constructing constant-height images.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 88 (2000), S. 4832-4839 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: A scanning near-field microscope that allows the fast acquisition of midinfrared absorption spectra is described. The microscope couples the nanoscale spatial resolution of a scanning probe microscope with the chemical specificity of vibrational spectroscopy. Key design elements of the microscope include a tunable broadband infrared light source; an infrared focal plane array-based spectrometer which allows parallel detection of the entire pulse bandwidth (200 cm−1); and a single mode, fluoride glass, near-field probe fabricated with a chemical etching protocol. Infrared transmission images of a micropatterned thin gold film are presented that demonstrate spatial resolution conservatively estimated to be λ/7.5 at 3.4 μm, in the absence of optical artifacts due to topography. Constant height mode images of a polymer nanocomposite demonstrate instrumental sensitivity to fractional transmission changes of 1×10−3. Near-field absorption spectra (λ=3.4 μm) of a 2 μm thick polystyrene film are presented which demonstrate the instrumental sensitivity required for high spatial resolution, near-field absorption imaging. These spectra are acquired in 2 s and indicate a film thickness detection limit for polystyrene of 200 nm. Measurements exploring the coupling between the infrared absorption magnitude and changes in tip–sample separation suggest that near-field absorption imaging is relatively insensitive to topographic artifacts.
    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 83 (1985), S. 2165-2169 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reactions of H2CO on a clean Ni(110) surface have been studied by high resolution electron energy loss spectroscopy (HREELS) and temperature programmed reaction spectroscopy (TPRS). At 95 K, H2CO adsorbs reactively, producing CO(a), CH3O(a), H(a), and small amounts of paraformaldehyde. Upon thermal treatment the CH3O decomposes to CO(a) and hydrogen while the paraformaldehyde reacts to form a surface intermediate which subsequently decomposes to CO2(g) and H2(g) at 350 K. Coadsorbed D2 is not incorporated into the CH3O(a) suggesting the methoxy is formed via a disproportionation reaction. Mixed paraformaldehyde and solid H2CO multilayers are formed at high exposures.
    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. 6710-6721 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The intensities of the stretch modes of CO adsorbed in bridge and top sites on Rh(100) are presented as a function of coverage, temperature, and during reaction with O. Following adsorption at 90 K, the top site is predominantly occupied at low coverages, and at 0.5 atomic monolayers (ML) only the top site is occupied and a c(2×2) low energy electron diffraction (LEED) pattern is observed. With higher coverages the bridge site is increasingly occupied, and at saturation a p(4(2)1/2×(2)1/2)R45° LEED pattern is observed. The occupations of bridge and top sites at a fixed (0.5 ML) total coverage are observed to vary reversibly when the temperature is linearly ramped from 87 to 371 K and back down to 90 K; the difference in the binding enthalpy of bridge and top sites is determined to be 1.10±0.06 kcal mol−1. The enthalpy difference between bridge and top sites is also obtained from temperature programmed EELS (TP-EELS) which follows the site occupations as the temperature is increased past desorption. Surface order is found to have a significant effect on the normalized intensities of CO in conventional EEL spectra. The normalized intensities in angle integrated spectra, obtained by modulating the voltage difference applied to the two halves of the split analyzer input lenses, are insensitive to changes in the degree of surface order. The effect of low frequency frustrated rocking motions of diatomic molecules on the temperature dependence of the intensities observed in electron energy loss spectroscopy (EELS) is discussed. TP-EELS of coadsorbed CO and O allows the direct observation of the changes in the occupation of CO binding sites during reaction, and the results are correlated with LEED and temperature programmed reaction spectroscopy (TPRS) measurements of the reaction. Segregation of the reactants during the reaction is important.
    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 83 (1985), S. 2569-2582 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The decomposition of methanol on a clean Ni(110) surface has been studied with temperature programmed reaction spectroscopy, low energy electron diffraction and temperature programmed electron energy loss spectroscopy: a new technique for the characterization of surface dynamic properties. Adsorption of methanol at 170 K results in the formation of a methoxy (CH3O) species. Near 270 K the methoxy decomposes into adsorbed hydrogen and carbon monoxide. For initial methoxy coverages greater than 0.20 monolayer (ML) the decomposition is rate limited by the desorption of product hydrogen. For initial methoxy coverages less than 0.20 ML the abstraction of the first methoxy hydrogen is rate limiting. This step is modeled by first order kinetics with an activation energy of 16 kcal mol−1 and a preexponential factor of 1012 s−1. A normal kinetic isotope effect (kH/kD〉1) is observed confirming that C–H bond scission is the rate limiting step at low coverages.
    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. 477-490 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The coadsorption of CO and H2 on Rh(100) at 100 K has been studied using temperature programmed desorption (TPD), low energy electron diffraction (LEED), electron energy loss spectroscopy (EELS), and temperature programmed EELS (TP-EELS). The preferred binding sites, long ranged order, and degree of segregation are dependent on the order of adsorption. When H2 is exposed to a CO preexposed surface, segregation of the surface species (atomic H and CO) is observed. The postdosed H2 causes isolated CO molecules to change from the top site to the bridge site, and compresses the c(2×2) CO islands that develop during the CO preexposure. When CO is exposed to a H2 saturated surface (one hydrogen per surface Rh atom) an intimately mixed c(2×2) CO and H structure is formed with all the CO molecules occupying the top site. Strong repulsive CO–H interactions in this mixed adlayer result in two new low temperature H2 TPD states. During the desorption of the lowest temperature H2 TPD peak, the c(2×2) LEED pattern streaks and the CO molecules shift from the top site to the bridge site. It is proposed that the preferred binding site for hydrogen in the c(2×2) bridge bonding CO structure is different from the fourfold hollow site preferred in the c(2×2) top bound CO structure. After the second H2 TPD peak, the remaining adsorbed H and CO segregate, and the CO regions are compressed. The compression is relaxed as the hydrogen desorbs. The development of the surface structures and their influence on the H2 TPD can be qualitatively understood in terms of precursor adsorption of both CO on H covered surfaces and H2 on CO covered surfaces, strong CO–H repulsions, and local poisoning of H2 dissociation by CO.
    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 98 (1993), S. 7651-7654 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rotational state and translational energy distributions of CO photodesorption products resulting from the 266 nm photolysis of Mo(CO)6 adsorbed on Si(111) 7×7 with coverages in the multilayer regime are reported. State-resolved measurements show two desorption components with highly disparate energy dispositions. Results for different surface temperatures indicate that the energy content in one component reaches quasi-equilibration with the surface temperature, which is attributed to collisional relaxation of nascent photodecomposition products within the adlayer. The other component exhibits disparate rotational and translational "temperatures'' that are significantly greater than, and independent of, the surface temperature. These nascent photodecomposition products are influenced by both energy quenching effects and dynamical constraints imposed by the existence of the adlayer.
    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 96 (1992), S. 2324-2338 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The results of a quantum-state-resolved study of the laser-induced desorption (LID) of NO from Si(111) 7×7 at a surface temperature of 100 K are reported. All aspects of the LID are found to be sensitive to the initial coverage. The coverage dependence indicates that there are two desorption mechanisms, one operative at low coverages that is quenched with increasing NO exposure, and one operative at high coverage. This report characterizes the low coverage channel. Most of the energy in the desorbed NO occurs as vibration and translation, with the rotations substantially cooler. The desorption is selective for production of the ground spin–orbit state. The energy partitioning shows strikingly little change as the desorption-laser wavelength was varied from 1907 to 355 nm. This, coupled with a quantitative study of the yield over the same photon energy range and selective coadsorption experiments, establishes that the desorption is specifically due to an interaction involving photogenerated holes in the rest-atom localized, intrinsic surface state of the 7×7 reconstructed surface. It is suggested that the surface state hole drives the desorption by neutralization of a NO−δ adsorbate.
    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 89 (1988), S. 5344-5345 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The internal state distributions of NO desorbed from a Pt(111) surface by visible and near-visible laser radiation (355, 532, and 1064 nm) were measured by laser-induced fluorescence. Non-Boltzmann rotational state distributions and inverted spin–orbit populations were observed and both were found to be relatively insensitive to the desorption-laser wavelength. It is suggested that the internal state distributions arise from the charge exchange processes occuring during desorption via a short-lived negative-ion resonance intermediate.
    Type of Medium: Electronic Resource
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