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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 7068-7078 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High resolution stimulated Raman spectroscopy (SRS) has been used to examine N2 and N2/He free jet expansions and also equilibrium samples of N2 from 15 to 110 K. The jet spectra show the formation of large liquid clusters which supercool and subsequently freeze to form crystalline β-N2 solid and, in He expansions, undergo a further transformation to a partially annealed α-N2 form. CW-SRS frequency and linewidth data obtained for equilibrium samples of the condensed phases of N2 yielded frequency–temperature relations used in deducing internal temperatures for the clusters produced in the expansion experiments. Analysis of the cooling curves indicates a mean cluster diameter of 35 nm and favors a prompt freezing process rather than a gradual conversion of liquid to solid in a single cluster on the microsecond time scale of the experiments. Supercooling limits of 34 to 44 K are deduced for the liquid, far below the triple point temperature of 63.2 K at which equilibrium samples freeze. Some evidence for surface versus bulk contributions to the spectra is seen in the asymmetric line shapes observed for liquid clusters in the condensation region. The results show that the high spectral and spatial resolution of nonlinear Raman methods such as SRS and CARS provide a unique probe of the condensation processes in free jet expansions.
    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 100 (1994), S. 3415-3421 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Microwave and infrared measurements have been made for the van der Waals complexes N2–CH3CCH and CO–CH3CCH, and their isotopomers. The infrared spectra are complicated by the effects of a slightly hindered internal rotation of the propyne unit. Tunneling motions arising from the N2 or CO molecules are not apparent in the infrared spectra, but in the case of N2 are seen in the microwave spectra. Analysis of the spectral data shows that the dimers are near slipped parallel in structure. Their dipole moments are almost parallel to the dimer b axis, with center-of-mass separations of 3.756(1) A(ring) for CO–CH3CCH and 3.708(2) A(ring) for N2–CH3CCH. (The uncertainties shown in parentheses are two standard deviations.) A simple model based on electrostatic interactions between rigid monomers gives dimer structures in agreement with the experimental assignments, and in conjunction with an approximate model of dispersion energy allows estimation of barriers to internal rotation.
    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 100 (1994), S. 262-270 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Positively and negatively charged coalescence products of C60 and C70 were characterized following pulsed laser desorption from fullerene thin films. Coalescence occurs by gas-phase reactions. Positive ions are generated by thermoionization of hot neutrals, while negative ions likely form by electron attachment to neutral species in the outermost region of the desorption plume. Thermoionization rate and surface-induced dissociation (SID) measurements are consistent with fullerene-like structures for coalescence products detected as positive ions.
    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 102 (1995), S. 540-543 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Laser desorption mass spectra of thin films of pure C60O were recorded in a range of equilibrium sample temperatures from 300 to 1100 K. On heating of the sample above 650 K a new peak corresponding to C−119 is detected in the anion mass spectrum which persists even after the sample is cooled to 300 K. Possible solid state reactions leading to the formation of C119 are discussed based on the mass spectrometric observations as well as temperature programmed decomposition measurements which were carried out for C60 and C60O samples. The results are discussed in connection with recently reported polymerization reactions of fullerene materials. © 1995 American Institute of Physics.
    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 101 (1994), S. 3243-3249 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: C60Ox, x=1–3 were prepared by exposing C60 solutions to ozone. After high performance liquid chromatography purification, these materials were studied by laser desorption time of flight mass spectroscopy. These mass spectra suggest that fullerene oxides undergo laser desorption induced coalescence more efficiently than pure C60. A correlation between the fragmentation of the desorbed parent species and the observed coalescence products both in yield and distribution suggests that efficient gas phase coalescence involves at least one reactive species, such as C58, produced by fragmentation of the desorbed fullerenes or fullerene derivatives.
    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 100 (1994), S. 5684-5695 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Neutral and positively charged clusters Mx(C60)z, where M=K/Rb and z=1–3 were prepared in pulsed molecular beams by laser desorption (266 nm) from preformed alkali metal fulleride thin films. Experimental results encompassed mass spectral characterization of beam abundance and in selected cases, determination of rough ionization potential brackets and elucidation of fragmentation pathways upon (i) unimolecular dissociation in gas phase and (ii) surface collision induced dissociation from Si(111). Results are contrasted with electrostatic model calculations as well as ab initio self-consistent field computations.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 98 (1994), S. 9683-9687 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 3990-3999 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    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 104 (1996), S. 3629-3637 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The interaction of C+60 and C+70 ion beams with a surface of highly oriented pyrolitic graphite was investigated by probing the ionization and fragmentation rates of scattered species within a time window of 20 μs following impact. Neutralization/reionization and fragmentation behavior was observed and followed by a pulsed deflection field applied to the surface at variable delays after the collision event. An almost complete collisional neutralization of the incident projectile was found. For an impact energy of 140–180 eV, a significant part of the scattered species was found to reionize by delayed electron emission within the experimental time window. The associated reionization and fragmentation kinetics were modeled with a system of differential equations assuming a simple unimolecular reaction diagram. Rate constants for delayed ionization and fragmentation were calculated as functions of internal energy and respective activation energies with the "finite heat bath'' model (Klots) and the Rice–Ramsperger–Kassel–Marcus expression, respectively. The calculated and measured (deflection field delay dependent) ion intensities were compared in a fit procedure. The best fit led to an activation energy for the fragmentation of C+60 (C+60→C+58+C2) of 6.6±0.5 eV. This translates to an activation energy of 7.1±0.5 eV for the fragmentation of neutral C60 (using the experimentally determined ionization potential of C58). For C+70 we obtained an identical (within error) activation energy for fragmentation (C+70→C+68+C2) of 6.6±0.5 eV. © 1996 American Institute of Physics.
    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 104 (1996), S. 3638-3650 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Fragmentation of various fullerenes was studied by surface impact on highly oriented pyrolytic graphite at collision energies Ecol of 150–1050 eV/molecule. The projectiles C+60, C+70, C+76, C+84, and C+94 were formed by laser desorption of chromatographically separated samples, while large carbon clusters C+94, C+110, C+164 were produced by laser-induced coalescence reactions. Except at the highest impact energies, the fragment distributions consist of even numbered C+n species with abundance maxima similar to those observed in fullerene synthesis. With increasing Ecol, we observe a size evolution in the fragment distributions characteristic of a sequential fragmentation process. Simulated fragment distributions based on statistical rate theory and a sequential C2 loss mechanism reproduce the experimental data well up to a maximum Ecol. They are used to determine the mean energy transfer during surface impact as a function of collision energy as well as its dependence on several experimental parameters such as the nature (cleanliness) of the target surface, the internal energy of the incident ion, and the incident fullerene size. Both internal and kinetic energy of the incident ion are found to contribute to the observed fragmentation although with different efficiencies. For the higher fullerenes we find a tendency towards increasing transfer efficiency of incident kinetic to internal energy with increasing projectile size. Finally, above a size-dependent impact energy threshold, a transition to a different high energy fragmentation process is indicated by changes in the fragment distributions. These go from exclusively even numbered fullerene fragments at low impact energy to smaller even and odd numbered C+n fragments at high Ecol. It is suggested that this change indicates the formation of high energy, nonfullerene isomers. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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