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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 7940-7946 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reactions of Rh+n cations, n=1–40, with C6H6 and C6D6 were investigated under single collision conditions in a Fourier-transform-ion-cyclotron-resonance mass spectrometer. For clusters with up to 18 rhodium atoms, dissociative chemisorption, accompanied by total or partial dehydrogenation in competition with nondissociative adsorption of an intact benzene molecule (physisorption) was observed. For clusters with n(approximately-greater-than)18 only the nondissociative adsorption was observed in the primary reaction step. Besides some enhancement of the nondissociative adsorption channel for cluster sizes n=9, 11, 12, and 13, deuteration has little effect upon the observed reactions. The atomic rhodium cation reacts after a few seconds induction time to an arene complex, which then forms a bis-arene complex in a secondary reaction step. Rhodium dimer alone exhibits some cleavage of the Rh–Rh bond, resulting also in the Rh–C6H+6 complex. © 1996 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 104 (1996), S. 3998-4004 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High resolution Fourier-transform ion cyclotron resonance (FT-ICR) mass spectroscopy is used to investigate reactions of large ionic water clusters H+(H2O)n and X−(H2O)n (n=1−100, X=O or OH). Reactions of the clusters with chlorine nitrate, important "reservoir compound'' involved in the stratospheric ozone chemistry, are investigated to evaluate the importance of heterogeneously catalyzed reactions for ozone depletion. It is found that reactions of both cationic and anionic clusters result in effective hydrolysis of chlorine nitrate and return of the more active hypochlorous acid, HOCl into the gas phase. The chemistry of clusters is discussed, and its validity and relevance as a model for "real life'' processes in the so-called polar stratospheric clouds (PSC's) is assessed. © 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 108 (1998), S. 5398-5403 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reactions of anionic niobium and rhodium clusters Mn−, M=Nb, Rh, n=3–28, with C6H6 are investigated under single collision conditions in a Fourier-transform ion-cyclotron-resonance mass spectrometer and compared with the results of previous studies on corresponding cationic species. This reveals strong effects of the cluster charge state on hydrocarbon activation as a function of cluster size. Both differences and parallels are observed for reactions of anions and cations. Niobium clusters with a given number of atoms react quite differently than those with a single atom more or less. The fact that almost identical such effects are in the present work found for anion clusters, as for cations with the same number of atoms but two less electrons, suggests that the observed reactivity patterns are more a function of the cluster shape and geometry, than of the details of their electronic structure. The variety of interesting trends and effects observed is interpreted in terms of simple physical models. © 1998 American Institute of Physics.
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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. 9664-9669 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The gas-phase reactions of sulphur cluster ions, cations S+n (n=1,...,8) and anions S−n (n=2,...,6) with NH3 have been studied by means of a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Relative and absolute reaction rate constants as well as reaction efficiencies have been determined. The S+4 cation has by the far highest reactivity with all other sulphur cations being significantly less reactive. Besides some fragmentation, no reactivity of the anions was found. Structural conclusions are made based on the present experiments, on previous extensive ab initio calculations, and on complementary experiments.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 4870-4884 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In a Fourier transform-ion cyclotron resonance mass spectrometer the gas phase reactivities of niobium clusters Nb+n (n=1–28) with molecular hydrogen, water, methane, ethane, n-propane, n-heptane, cyclohexane, acetylene, ethylene, allene, benzene, propene, toluene, xylene, and acetonitrile were investigated under single collision conditions as well as the reactivities of oxidized niobium cluster cations with ethylene and benzene. The reactions of larger clusters with a variety of unsaturated hydrocarbons are believed to proceed via long lived "physisorbed'' addition intermediate complexes, which subsequently rearrange to form "chemisorbed,'' extensively dehydrogenated final products. The overall reaction seems to proceed with near collision rates, almost independent of cluster size. In some cases also the physisorbed primary products are stabilized and detected. Their yields depend sensitively on the specific nature of the reactant, and on the niobium cluster size n. Fully saturated hydrocarbons unable to form the long lived complexes are unreactive with respect to the larger (n(approximately-greater-than)7) Nb+n clusters. Smaller clusters with n≤7 seem to react by a different, prompt reaction mechanism. The rate of this reaction steeply decreases, and the degree of product dehydrogenation increases with n. © 1995 American Institute of Physics.
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