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  • 11
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 4976-4987 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In a crossed molecular beam experiment, time-of-flight distributions of NH3 molecules scattered from He have been measured as a function of the deflection angle at E=97.7 meV. The spectra, which cover a center-of-mass angular range from 97° to 168° show appreciable rotational energy transfer in the backward direction. These data, which are sensitive to the repulsive anisotropy of the interaction potential, are used together with the diffraction oscillations of total differential cross section to determine a new rigid rotor potential surface for NH3–He. The potential is constructed by combining large basis set self-consistent-field (SCF) calculations with damped long range dispersion coefficients. The two free parameters of the damping function are determined by fitting the measured data to calculations using the quantal coupled states approximation. The potential is in reasonable agreement with calculations where correlation effects are included and reproduces the measured second virial coefficients.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 1042-1044 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 9428-9437 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Classical Monte Carlo and molecular dynamics (MD) simulations were carried out to investigate the structures, the infrared spectra, and the rigid–nonrigid transitions of small methanol clusters (CH3OH)n for n=3–6. The study was motivated by experimental results for these clusters from size specific infrared (IR) dissociation spectroscopy. The MD simulations revealed the following transitions: The trimer passes from a rigid ring configuration into a series of nonrigid open chain structures starting at 197 K. For n=4 and 5 such transitions occur between rings and rapidly fluctuating ring structures at T=357 and 243 K, respectively. For n=6 first a pure isomeric transition between the two energetically lowest isomers of S6 and C2 symmetry is found at 35 K, and then a similar transition to a nonrigid behavior as is observed for n=4 and 5 is seen at 197 K. The measured spectra display in all cases the rigid lowest energy configurations.
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 1810-1821 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Computer simulation methods are used to calculate the vibrational spectra of hydrogen fluoride clusters, and the liquid, in the intramolecular stretching region. A semiclassical approach, in which Monte Carlo and molecular dynamics simulations are analyzed using quantum vibrational calculations, is a considerable improvement over dipole correlation function methods. Comparisons with experimental data show that induced dipole interactions play an important role in determining spectral shifts. A simple Drude oscillator model of polarization allows the spectral shifts to be obtained correctly, but at the expense of overestimating structural correlations in the liquid.
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 4250-4255 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ammonia clusters that are generated in a supersonic expansion with He are size selected by a scattering process with He atoms. By measurements of angular dependent mass spectra and time-of-flight distributions at all fragment masses, the complete fragmentation pattern for electron impact ionization of clusters from the dimer to the pentamer are obtained for electron energies of 70 eV. The dimer fragmentation which is dominated by the NH+4 ion (0.58) can be explained completely by fast ion–molecule reactions of the monomer fragments with the partner molecule. For the larger clusters up to n=11 the NH+4 ion is still the largest fragment channel. The other protonated ions NH+4(NH3)x start to contribute to the fragmentation with increasing cluster size but never exceed the contribution at mass 18 amu.
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 6017-6029 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Size-selective infrared photodissociation spectra of (CH3OH)n clusters from n=2 to n=9 were measured near the absorption band of the C–O stretching mode of the monomer at 1033.5 cm−1 . The experiments were carried out in a molecular-beam apparatus in which the clusters are generated in a supersonic expansion and afterwards size selected in a scattering experiment with helium atoms. The internally excited clusters are dissociated by the radiation of a cw CO2 laser in a new antiparallel arrangement of the scattered cluster beam and laser beam. The observed spectra vary from the dimer, for which a double-peak structure appears, to the single-peak spectra of the trimer, tetramer, and pentamer which are continuously shifted to higher frequencies. A special transition is seen from the pentamer to the hexamer, for which again a double-peak structure is observed which continues to larger clusters. Applying an intermolecular model potential, a correlation between the observed spectra and the cluster configuration of minimum energy is derived. The line shifts of the dimer to the red and blue are caused by the nonequivalent position of the donor and acceptor in the hydrogen bond. The next three larger clusters are nearly planar rings, while from the hexamer onwards, only distorted rings and similar isomeric structures appear. These calculations together with the evaluation of the integrated dissociation cross section show that only internally excited dimers and trimers can be dissociated with one or two CO2 laser photons, respectively.
    Type of Medium: Electronic Resource
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  • 17
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 6477-6493 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In order to address the problem of three-body interactions in gas–surface scattering, we considered the collision of a He atom with the (0001) surface of graphite coated by a monolayer of Xe. To eliminate the uncertainties connected with errors in the two-body He–Xe interaction, we determined the latter by crossed-beam differential collision cross-section measurements performed at two energies (67.2 and 22.35 meV). These scattering data together with room-temperature bulk diffusion data are then fitted with a Hartree–Fock–dispersion–type function to yield an interaction potential that explains most of the properties of this system within the experimental errors and represents an improvement on previously published He–Xe potentials. Helium diffraction measurements are then carried out from the Xe overlayer and the dependence of the specular intensity from the angle of incidence is carefully determined. Further, a He–surface potential is constructed by adding together the following terms: (1) the He–Xe pairwise sum, (2) the long-range He–(0001)C interaction, (3) the three-body contribution generated by the Axilrod–Teller–Muto term, (4) the so-called surface-mediated three-body interaction He–Xe–(0001)C first considered by A. D. McLachlan [Mol. Phys. 7, 381 (1964)], and finally (5) a small correction which is meant to take into account the nonstationary nature of the surface. Using this potential, well-converged close-coupling scattering calculations are carried out, and their results compared with the data. In general, good agreement is obtained. The agreement can, however, be improved by (a) an increase of about 30% in the contribution of three-body forces, (b) the lowering of the He–graphite long-range attraction coefficient by about 15%, or (c) a reduction of the two-body interaction well depth of 1.6% (the experimental error) together with any combination of the factors under (a) and (b) reduced by an adequate amount. Elimination of the contribution of the graphite surface by studying Xe multilayers is hindered by the uncertainties in the "thermal correction'' [point (5) above] which, due to the multilayer increased "softness,'' becomes an appreciable source of uncertainty.
    Type of Medium: Electronic Resource
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  • 18
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 3028-3031 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The fragmentation of ammonia dimers by electron impact ionization is investigated by preselecting the neutral species using scattering and spectroscopic methods. In the first experiment, the measured angular and velocity dependence of the ammonia cluster scattered from a helium beam is used to separate the dimer from the other contributions. In the second experiment, the rotationally resolved spectrum obtained by microwave electric resonance technique is used to label the dimer. The ratio of the ion intensities m=18 (NH+4) to m=17 (NH+3) amu is 1.3 and 1.8, respectively. In the case of scattering, the result is independent of the initial state distribution of the dimer. The remaining difference is attributed to the different ion sources. This remarkable result is explained in terms of simple models based on the structural change from the neutral to the ionized configuration and the fragmentation pattern of the monomer.
    Type of Medium: Electronic Resource
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  • 19
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 6419-6432 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In crossed molecular-beam experiments, three type of cross sections have been measured: Total differential cross sections with well-resolved diffraction oscillations for oD2–NH3 at E=95.9 and 111.3 meV, differential energy-loss spectra for ND3–oD2 at E=118.3 meV which cover the center-of-mass (c.m.) angular range from 85° to 170° and are obtained by time-of-flight (TOF) analysis, and state-to-state integral cross sections for oNH3–H2 and pNH3–H2 at E=75 meV for many final rotational states which are detected by resonance enhanced multiphoton ionization. These data which are mainly sensitive to the anisotropy of the potential energy surface are well reproduced by quantum calculations in the coupled-states approximation. The potential is constructed by combining large basis-set self-consistent-field (SCF) calculations with damped long-range dispersion coefficients. The two free parameters of the damping function are fitted to a restricted set of configuration interaction (CI) calculations.
    Type of Medium: Electronic Resource
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  • 20
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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