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  • 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 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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  • 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 113 (2000), S. 5053-5057 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Collisions of singly and multiply charged ions C60z+ (z=1,2,3,4,5) with a hydrocarbon-covered stainless steel surface have been investigated; product ions of fragmentation and pickup reactions were determined as a function of the collision energy (100–500 eV) and the projectile charge z. All ions scattered off the surface are singly charged. The extent of fragmentation increases with the collision energy and the projectile charge. However, the increase of fragmentation with the charge of the projectile is less pronounced than expected from a full conversion of electronic energy, gained in the neutralization process, into internal energy of the ion. © 2000 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 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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  • 6
    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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  • 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 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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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 8674-8679 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Electron impact ionization of C60 and C70 has been studied as a function of electron energy in the threshold region using a crossed molecular beam/electron beam double focusing sector field mass spectrometer system. Appearance energies have been determined (using a special threshold extrapolating procedure) for Cz+60-2m and Cz+70-2m ions with z ranging from 1 to 4 and m from 0 to 4, respectively. Whereas the different charge states of the parent ions of C60 and C70 have the same appearance energies within the experimental error bars, the fragment ions of C70 show slightly higher values than their C60 counterparts due to an increased kinetic shift. The presently deduced ionization energies for the C60 parent ions are in excellent agreement with previously reported reliable data for Cz+60 ions (previous data are available only up to z is 3). In contrast, these experimental values disagree strongly with a theoretical calculation by Yannouleas and Landman predicting an approximately linear dependence of the ionization energy on the charge state z, i.e., the experimental values deviate strongly from linearity with increasing charge.
    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 88 (1988), S. 6884-6888 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Electron attachment and electron impact ionization of SF6 and SF6/Ar clusters have been investigated in a molecular beam/electron impact ion source/mass spectrometer system. Positive ion mass spectra of neat SF6 clusters contain [(SF6)n⋅SFx]+ fragment ion series with 0≤x≤5 and in addition [(SF6)nS2F5]+ ions which have to be formed via international ion molecule reactions. Positive ion mass spectra of mixed SF6/Ar clusters include ion series of nonstoichiometric fragment ions (SF5⋅Arn)+, (SF6⋅SF5⋅Arn)+, [(SF6)2⋅SF5⋅Arn]+, and, in addition, stoichiometric ions comprised of (SF6⋅Arn)+ and [(SF6)2Arn]+. These stoichiometric ions are only present with n≥3. Electron attachment to neat SF6 clusters gives rise only to stoichiometric (SF6)−n ions, whereas attachment to mixed SF6/Ar clusters yields ion series consisting of (ArnSF6)−, [Arn(SF6)2]−, and [Arn⋅(SF6)3]−. This indicates that the dissociative channel into SF−5 present in the monomer is efficiently quenched in case of clusters. The negative ion mass spectra show in contrast to the positive ion mass spectra a strong dependence on electron energy due to a strong resonance of the attachment cross sections near zero electron energy.
    Type of Medium: Electronic Resource
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