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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 7494-7498 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The kinetics of NH3 and ND3 desorption from Cu(001) surface have been measured by time-resolved electron energy loss spectroscopy. The desorption precess is observed to be characterized by pseudo-first-order kinetics. The desorption energy and the prefactor have been determined for both NH3 and ND3. The prefactors are unusually low as compared to those observed for simple diatomic molecules. Moreover, we observed an unusual behavior consistent with an isotope kinetic compensation effect. Both of these observations can be explained within the context of transition state theory by the interplay between isotopic masses and the shifts of frustrated vibrational modes of adsorbed molecules. Our results imply that the conventional Arrhenius form would not be precisely applicable to molecular desorption, if a large enough temperature range could be measured, particularly for hydrogen-containing molecules.
    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. 7964-7971 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present time-resolved electron energy loss spectroscopy (EELS) results for the desorption of submonolayer coverages of H2O and D2O from Ag(011). The measurements were performed isothermally and effectively at constant coverage. At coverages above a few percent of a monolayer, we observe that the desorption is characterized by zero-order kinetics. That is, the desorption rate is independent of coverage. We hypothesize that this results from the formation of two-dimensional water islands on the surface at all coverages and temperatures measured. The desorption process is governed in part by the dissociation of water from the edges of these islands. Rapid diffusion on the surface maintains a quasiequilibrium between the molecules bound to islands and isolated adsorbed water molecules, thereby leading to pseudo-zero-order kinetics. This result is interpreted upon general thermodynamic grounds, and also using a simple kinetic model which leads to pseudo-zero-order desorption kinetics. An unusual hydrogen kinetic isotope effect is reported which lends support to our interpretation.
    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 95 (1991), S. 5355-5363 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present time-resolved electron energy loss spectroscopy measurement of isothermal desorption of NH3 and ND3 from Cu(001) as a function of coverage. The desorption process is characterized by pseudo-first-order kinetics. The pseudo-first-order rate constant increases approximately exponentially as a function of adsorbed ammonia coverage. The results of an analysis based on a quasiequilibrium approximation which expresses the desorption rate in terms of a virial expansion in adsorbate coverage are reported. This demonstrates that the intermolecular interactions are dominated by short range repulsive lateral interactions, in qualitative accord with expectations of dipolar interactions. The results also suggest the existence of longer-range attractive interactions.
    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 99 (1993), S. 4152-4159 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The theory of substrate-mediated dispersion interactions is applied to analyze a set of quasiequilibrium measurements of adsorption isobars and desorption isotherms of the CH4/Ag(011) physisorption system. The theory provides for the construction of an adsorbate intermolecular potential from the gas phase potential, with the spacing between the metal surface and the adsorbed layer as the sole adjustable parameter. The best fits to the kinetic and thermodynamic data yield a consistent intermolecular potential, with a well depth of approximately two-thirds of the free space value. The limited dynamic range of the measurements does not permit a determination of the form of the intermolecular potential. However, the good agreement of the theory with both data sets lends strong support for the quasiequilibrium model, and supports the proposition that the properties of physisorbed layers can be predicted using gas phase potentials while accounting for substrate-mediated dispersion interaction effects.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Physics of Fluids 29 (1986), S. 941-951 
    ISSN: 1089-7666
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The drop size distribution was measured from back-lighted spark photographs at the edge of steady sprays in the immediate vicinity of the nozzle exit. The conditions of these liquid-into-gas sprays were such that the outer surface of the liquid jets broke up into small drops at the nozzle exit. The objective was to elucidate the mechanism of breakup. At room temperature, n-hexane and n-tetradecane at pressures from 2.86 to 9.76 MPa were injected into gaseous nitrogen at 1.48 to 2.86 MPa through three straight cylindrical nozzles of different diameters, 127 and 335 μm, and length-to-diameter ratios, 4 and 10. In all cases, the drop sizes could be fitted satisfactorily with a chi-square distribution with degree of freedom equal to 28. The Sauter mean drop diameter and other average diameters were found to decrease with increasing injection velocity and decreasing liquid surface tension, to be insensitive to nozzle diameter and length, and to increase slightly with increasing gas density. The trends and magnitudes are in agreement with those predicted by the supplemented aerodynamic theory of surface breakup if it is assumed that between the jet surface where the drops are formed, that is not visible, and the edge of the spray, where the measurements were made, drops undergo collisions and coalescence. In this region of dense sprays, drop coalescence leads to a rapid increase in drop size, particularly in high gas densities.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 62 (1991), S. 1256-1262 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: A new high-resolution electron energy-loss spectrometer based on the dispersion compensation (DC) concept has been designed, built, and tested. The parallel processing inherent in DC has allowed us to attain signal levels two orders of magnitude in excess of conventional designs while operating at comparable resolution. This is consistent with expectations based on simple model calculations. The resolving power of the spectrometer is not as good as theoretically predicted probably due to uncontrolled beam angle effects. Initial tests on a variety of systems are presented. We analyze the strengths and weaknesses of the design and suggest future improvements.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Experimental Cell Research 208 (1993), S. 241-247 
    ISSN: 0014-4827
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Biology , Medicine
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Journal of Electron Spectroscopy and Related Phenomena 54-55 (1990), S. 551-560 
    ISSN: 0368-2048
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 6 (1992), S. 209-213 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Ferulic acid, sinapinic acid and 2,5-dihydroxybendoic acid (DHBA) have been tested as matrix materials for matrix-asserted laser desorption of the pure oligonucleotide pd(T)12 and a mixture of oligonucleotides pd(T)12 through pd(T)18 using pulsed 337 nm radiation combined with reflecting time-of-flight mass spectrometry. The three matrix materials are compared with respect to obtainable mass resolution, degree of fragmentation, and adduct formation, as well as the highest mass resolution.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Publication Date: 2013-11-18
    Print ISSN: 0027-8424
    Electronic ISSN: 1091-6490
    Topics: Biology , Medicine , Natural Sciences in General
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