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  • 1995-1999  (10)
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Year
  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3548-3558 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Highly monochromatized electrons (with energy distributions of less than 30 meV FWHM) are used in a crossed beam experiments to investigate electron attachment to oxygen clusters (O2)n at electron energies from approximately zero eV up to several eV. At energies close to zero the attachment cross section for the reaction (O2)n+e→(O2)m− (for m=1, 2, and 3) rises strongly with decreasing electron energy compatible with s-wave electron capture to (O2)n. Peaks in the oxygen attachment cross sections present at higher energies ((approximate)80 meV, 193 meV, 302 meV) can be ascribed to vibrational levels of the anion populated by attachment of an electron to a single oxygen molecule within the target cluster via a direct Franck–Condon transition from the ground vibrational state v=0 to a vibrational excited state v′=7,8,9,... of the anion produced. The vibrational structures observed here for the first time can be quantitatively accounted for by model calculations using a microscopic model to examine the attachment of an electron to an oxygen molecule inside a cluster. This involves (i) molecular dynamics simulations to calculate the structure of neutral clusters prior to the attachment process and (ii) calculation of the solvation energy of an oxygen anion in the cluster from the electrostatic polarization of the molecules of the cluster. The occurrence of this polarization energy at the surface of larger clusters explains the appearance of an s-wave capturing cross section at 0 eV and the slightly smaller spacings (compared to the monomer case) between the peaks at finite energy, as observed experimentally. The relative transition probabilities from the ground state of the neutral oxygen molecule to the different vibrational levels of the anion are obtained by calculating the corresponding Franck–Condon factors thereby resulting in a reasonable theoretical fit to the observed yields of negatively charged oxygen molecules and clusters. © 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 111 (1999), S. 2770-2778 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The occurrence of two different chemical reactions initiated by the surface impact of acetone dimer, trimer, and tetramer cations (energy 20–70 eV) on a stainless-steel surface (covered with hydrocarbons) was observed. The reaction product is the protonated acetone ion, formed in (i) an intracluster ion–molecule reaction, and in (ii) a hydrogen pickup reaction of the cluster ion with the surface material. Only the monomer product ions (and small amounts of their dissociation products) could be observed; the spectra did not show any presence of clustered product ions. A simple model based on the Brauman double-well potential is suggested to explain the formation of the two product ions. In accordance with predictions from molecular dynamics simulations, this appears to be the first observation of competitive chemical reactions of a cluster ion driven by energy transfer in a surface collision. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 15428-15437 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    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 108 (1998), S. 963-970 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We used mass spectrometric techniques in conjunction with the ion deflection method to determine the kinetic energies of Cn+ fragment ions (58≥n≥4) produced by controlled electron impact on C60 under single collision conditions. The recorded ion beam profiles for the various fragment ions were analyzed using two independent methods. One method extracts the average kinetic energy of the fragment ion under study from the measured half-width of the ion beam profile (half-width method), whereas the second method analyzes the entire measured beam profile (profile method). For each Cn+ fragment ion, the kinetic energies obtained were interpreted assuming two possible formation pathways, (i) the fission of the excited parent C60+ ion in a single-step, two-fragment break-up, C60+→Cn++C60−n and (ii) the sequential decay of excited C60+ into Cn+ via the successive removal of Cm units (m=1, 2, or 3). Both the half-width method and the profile method yield very similar results for the kinetic energies of the Cn+ fragment ions for both formation mechanisms, viz., an average kinetic energy of roughly 0.45 eV in the case of the single-step fission and a linearly increasing average kinetic energy from 0.43 eV for the formation of C58+ to roughly 12 eV for the formation of C4+ in case of the sequential decay mechanism (in this case an essentially constant energy of also about 0.45 eV was obtained for the last fragmentation step in each case, which was confirmed by a third method using a fitting procedure). These results will be discussed in the context of the most likely fragmentation mechanism leading to the formation of the various fragment ions. © 1998 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 107 (1997), S. 6246-6256 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have obtained direct mass spectrometric evidence that fullerene ions C60z+ (z=1, 2, or 3) and C58z+(z=1,2) undergo unimolecular dissociation by sequential emission of twoC2 units, on a time scale of 10−5 s. Moreover, a comparison of experimental and theoretical breakdown graphs reveals that unimolecular formation of C56+ from the C60+ parent ion within a given observational time window is dominated by successive loss of C2; direct C4 loss does not contribute significantly. This conclusion is not affected by uncertainties in our knowledge of the energetics of C2 vs C4 loss. © 1997 American Institute of Physics.
    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 108 (1998), S. 990-1000 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using high sensitivity two sector field mass spectrometric techniques (in particular MIKE scans) we have studied quantitatively (and systematically) the energetics of the superasymmetric spontaneous decay reactions (involving either C2+ or C4+ loss) of triply, quadruply, quintuply, and sextuply charged carbon clusters ions Cnz+ in the size range from n=36 up to n=70. From the kinetic energy release data determined, the apparent intercharge distance has been derived using different models including the simple point charges model, the movable charges model and the charged conducting sphere model. As in earlier but less extensive studies the intercharge distance obtained is for all three models used larger than the cage radius of the respective precursor fullerene ion. It is shown that this and other experimental results are only compatible with the recently suggested auto charge transfer (ACT) reaction as the decay mechanism responsible for the superasymmetric charge separation reactions, whereas two other conceivable decay mechanisms (ball-chain-propagation and decay of charged conducting liquid sphere) are not consistent with all of the experimental fingerprints observed. © 1998 American Institute of Physics.
    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 107 (1997), S. 8955-8962 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using a crossed electron-molecule beam ion source in combination with a quadrupole mass spectrometer we have studied the electron energy dependence of the dissociative attachment process CHCl3+e→Cl− at electron energies from about 0 to 2 eV and in a target gas temperature range of about 300–430 K. The energy resolution and working conditions of this newly constructed crossed beams machine have been characterized using CCl4 as a test and calbrant gas. Utilizing the improved energy resolution of the present experimental setup (which allows measurements with FWHM energy spreads down to below 5 meV) it was possible to determine the accurate shape and magnitude of the cross section function in the low-energy range. This leads to the conclusion that between an electron energy of about 20 and 130 meV the reaction proceeds via deBroglie s-wave capture, whereas at higher energy (above about 0.4 eV) autodetachment plays a significant role. Moreover, the present measurements allow us to clarify previously reported differences in the absolute cross section, the number of peaks and in the energy position of these peaks. Finally, by analyzing the measured strong temperature dependence of the cross section close to zero electron energy the activation barrier for this dissociative attachment was determined to be 110±20 meV in good agreement with thermochemical data from swarm experiments performed under thermal equilibrium. Taking into account the present results it is also possible to discuss the mechanism for the existence of the second peak. © 1997 American Institute of Physics.
    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 105 (1996), S. 1880-1896 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Electron impact ionization of C60 and C70 was studied using a molecular/electron beam ion source in combination with a two sector field mass spectrometer operated in the ion beam deflection mode. Relative partial ionization cross sections for the production of singly and multiply charged parent ions (up to charge state z=4) and fragment ions (down to C+44 in the case of C60 and down to C2+50 in the case of C70) were determined from threshold up to 1000 eV electron energy. Absolute partial and total ionization cross sections are obtained using a novel approach for the absolute calibration involving an intercomparison of the cation with the anion yield. The results obtained reveal not only an anomalous large parent ion cross section as compared to other ionization channels [e.g., σ(C+60/C60) is more than a factor of 30 larger than σ(C+58/C60)] but also anomalies for the production of multiply charged parent and fragment ions. For instance, the maximum cross section for the formation of C2+60 amounts to 30% of the maximum C+60 cross section and that of C2+70 to about 50% of C+70. Moreover, for all fragment ions, the formation of the doubly charged fragment ions has a larger cross section than that of the respective singly charged fragment ion. These peculiar features of the kinetics of electron impact ionization of C60 and C70 are related to the specific electronic and geometric structures of these fullerenes. The present absolute cross-section data for the summed up partial cross sections are in good agreement with a recent semiclassical calculation from our laboratory. © 1996 American Institute of 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. 1225-1231 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using recently measured accurate relative partial ionization cross section functions for production of the C60 fragment ions C+58 through C+44 by electron impact ionization, we have determined the respective binding energies BE(C+n–C2), with n=58,...,44, using a novel self-consistent procedure. Appearance energies were determined from ionization efficiency curves. Binding energies were calculated from the corresponding appearance energies with the help of the finite heat bath theory. Then using these binding energies we calculated with transition state theory (TST), the corresponding breakdown curves, and compared these calculated ones with the ones derived from the measured cross sections. The good agreement between these breakdown curves proves the consistency of this multistep calculation scheme. As the only free parameter in this procedure is the binding energy C+58–C2, we studied the influence of different transition states chosen in the determination of this binding energy via TST theory and iterative comparison with breakdown curve measurements. Based on this study we can conclude that extremely loose transition states can be confidently excluded, and that somewhat looser transition states than those used earlier result in an upward change of the binding energy of less than 10% yielding an upper limit for the binding energy C+58–C2 of approximately 7.6 eV. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Hyperfine interactions 99 (1996), S. 175-191 
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Highly-charged fullerene ions C 60 z+ and C 70 z+ with charge states up to z=7 have been produced in an electron impact ion source of a two sector field mass spectrometer by using ion source operating conditions similar to those used in EBIT sources. The stability of these ions was investigated quantitatively in the two field free regions of the mass spectrometer. It was found that besides C2 evaporation the dominant fission process for ions with charges larger than +2 is the loss of a charged C 2 + unit via a super-asymmetric charge separation reaction C 60 z+ → C 58 (z−1)+ +C 2 + and C 70 z+ → C 68 (z−1)+ +C 2 + , respectively. The most important finding from these studies is that this super-asymmetric dissociation reaction proceeds via a three stage reaction sequence involving an electron transfer reaction at the second stage between a receding C2 unit and the remaining highly-charged fullerene cage.
    Type of Medium: Electronic Resource
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