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  • 1985-1989  (4)
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Year
  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 1111-1117 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The van der Waals (vdW) complexes consisting of benzonitrile and various partner species were formed in a free jet and their laser-induced fluorescence (LIF) spectra were recorded. For all the species chosen as partners (Ar, Kr, N2O, CF3H, and H2O), the LIF spectra showed a red shift relative to that of benzonitrile monomer. The spectral shift increased with increasing dipole moment of the partner species owing to the large dipole–dipole interaction between the partner species and benzonitrile whose dipole moment amounts to 4.14 D. With the aid of computer simulation, the rotational contours of the LIF spectra of the benzonitrile dimer and benzonitrile–Ar complex were analyzed. The dimer was found to be in planar form with the two CN groups facing each other in an antiparallel geometry, whereas in the Ar complex the Ar atom lies over the benzene ring slightly leaning toward the CN group.
    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 88 (1988), S. 4739-4747 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The vibrational and rotational state distribution was measured for NO produced from the reaction O(1D)+N2O→2NO via a reactant pair O(1D)⋅N2O, which, in turn, formed by the 193 nm photolysis of the N2O dimer. The dimer was generated by the supersonic expansion through a pulsed nozzle. The distribution was determined by using the laser-induced fluorescence of NO on its A–X transition. The rotational distribution was of the Boltzmann type characterized by a low temperature, 60–100 K, at each vibrational level measured. The vibrational distribution was found to be composed of the two components, one very cold and the other relatively hot. The experiment using an isotopically labeled N2O revealed that the vibrational energy was not equally distributed over two kinds of NO; the NO originally present in N2O was vibrationally cool while that formed from O(1D) and the terminal nitrogen of N2O was vibrationally hot. These results indicate that the reaction occurring is the abstraction of the terminal nitrogen by O(1D). The low rotational temperature, which sharply contrasts with the extremely high rotational excitation observed for the ordinary bimolecular reaction, can be rationalized by considering the geometrical difference in the encounter between the O(1D) atom and N2O. This fact, in turn, indicates that the product energy distribution is significantly affected by the orientation in the reactive encounter.
    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 86 (1987), S. 1118-1124 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dispersed fluorescence spectra of the van der Waals (vdW) complexes consisting of benzonitrile and various partner species were observed in a free jet following a single vibronic level (SVL) excitation. For the vdW complexes with atomic species (Kr and Ar), the fluorescence was found to come from the initially prepared state and/or from the monomer produced by vibrational predissociation. On the contrary, in the case of benzonitrile–molecule complexes (H2O, N2O, and CF3H), only the fluorescence from the relaxed vdW molecule was observed. These features are interpreted in terms of a simple general scheme of predissociation. Vibrational predissociation is considered to be a composite of the four processes: (1) radiative decay of the prepared state; (2) intracomplex vibrational energy transfer producing a relaxed vdW complex; (3) radiative decay of the relaxed vdW complex; and (4) dissociation of the relaxed vdW complex. The difference in fluorescent state between atomic and molecular vdW complexes are caused by the competition among these four processes. The relative importance among these processes is strongly dependent on the state density of the vdW modes which in turn reflects the degrees of freedom of the partner species.
    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 86 (1987), S. 5491-5499 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reaction O+(NO)2 was studied by use of a crossed-beam apparatus. An (NO)2 beam generated by the supersonic expansion crossed at right angles with a collimated effusive beam containing oxygen atoms which were formed by microwave discharge. The product NO@B|2 was detected by the chemiluminescence. The angular distribution of the product was measured by an angle-resolved emission detection technique. The distribution has forward and backward peaks with respect to the oxygen atom incidence and indicates the occurrence of an intermediate complex in the course of the reaction. The angular velocity distribution, as well as the onset of the chemiluminescence, indicates that the reaction exothermicity appears mostly as internal energy of NO*2 . The remaining energy flows into the product translation and rotation; the vibrational freedom of the third-body molecule is not effective as an energy absorber. The emission intensity was found to decrease with increasing relative collision energy. A sharp drop of the intensity was observed at 2 kcal/mol of collision energy, which is in good agreement with the bond energy of the NO dimer.
    Type of Medium: Electronic Resource
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