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  • 1
    Electronic Resource
    Electronic Resource
    Infrared absorption and microwave–infrared double resonance studies of Ne⋅OCS molecular beams (1987)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 1670-1678 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Infrared absorption spectra for molecular beams of Ne⋅OCS have been observed with a diode laser for the vibrational transition near 2062 cm−1 correlating with the monomer ν3 mode. The linewidths were ∼150 MHz (FWHM), giving rotationally resolved spectra and allowing the upper and lower vibrational state A, B, and C rotational constants to be determined along with the frequency of the band origin. No broadening in excess of that expected from Doppler effects and laser linewidth was observed, setting a lower limit of 10−9 s on the lifetime of the upper state. Rotational transitions for the vibrational ground state were observed by microwave–infrared double resonance experiments. The ∼150 kHz linewidths in these experiments increased the precision of the rotational constants and permitted the quartic centrifugal distortion constants for the ground state to be determined. The effective structure of the Ne⋅OCS complex was calculated from the rotational constant data. The vibrational frequency and structural results are discussed in relation to similar work on other rare gas–OCS complexes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.452758
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  • 2
    Electronic Resource
    Electronic Resource
    A model for the energy levels of rare gas–spherical top van der Waals complexes (1994)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 7042-7050 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A model for the rovibrational energy levels of a complex formed between a rare gas atom and a spherical top molecule is developed, specifically for a tetrahedral XY4 molecule in its ground and its triply degenerate vibrational states. Under the assumption that the tetrahedral molecule remains undistorted upon complexation, a large amount of the tetrahedral symmetry is retained in the complex. Using symmetry adapted terms to represent the anisotropy of the intermolecular potential, the perturbations to the energy levels of the tetrahedral molecule caused by the intermolecular potential have been considered. Correlation diagrams showing the pattern of these internal rotor states between the free rotor and rigid molecule limits have been constructed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.466904
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  • 3
    Electronic Resource
    Electronic Resource
    Spectroscopy and dynamics of rare gas–spherical top complexes. The infrared spectrum of the ν3 band of argon–silane (1994)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 7051-7060 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The infrared spectrum of Ar–SiH4, a rare gas–spherical top van der Waals complex, has been recorded in the vicinity of the silane ν3 triply degenerate stretching vibration ∼2189 cm−1. A complex, dense spectrum is observed, and this is due to the observation of 12 bands with origins corresponding to transitions between different internal rotor states of the silane molecule within the complex. From the analysis of the rotational structure within each band, the average argon–silane separation is determined to be 4.043 A(ring) in the ground vibrational state and 4.046 A(ring) in the excited vibrational state with v3=1. Using a model developed previously and a very simple form for the intermolecular potential, these 12 bands have been assigned and an effective anisotropic intermolecular potential for the internal rotation of the silane molecule within the complex has been determined. The vibrational anisotropy responsible for lifting the threefold degeneracy of the ν3 vibration is found to be fairly small, of the order of 1 cm−1, while the rotational anisotropy is much larger, of the order of 90 cm−1.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.466905
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  • 4
    Electronic Resource
    Electronic Resource
    Spectroscopy and dynamics of rare gas–spherical top complexes. II. The infrared spectrum of the ν3 band of Ne–SiH4 ( j=1←0 and j=0←1 transitions) (1996)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 5391-5405 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The infrared spectrum of the rare gas–spherical top complex Ne–SiH4 has been recorded in a supersonic jet in the region of the SiH4 ν3 triply degenerate stretching vibration at ∼2189 cm−1. In contrast to the previously measured Ar–SiH4 spectrum which showed almost equal rotational spacings within each band (corresponding to transitions between different internal rotor states of SiH4 within the complex), the Ne–SiH4 spectrum is complex with no obvious regular band structure. However, by analogy with the Ar–SiH4 spectrum, four bands of the Ne–SiH4 have been assigned and analyzed in terms of Hamiltonians incorporating Coriolis interaction between the angular momentum of the SiH4 monomer unit and the overall end over end rotation of the complex. These bands correlate with the SiH4 R(0) (K=0←0, K=1←0) and P(1) (K=0←0, K=0←1) transitions. Derived rotational constants demonstrate that the neon–silane separation (∼4.13 A(ring) in the ground vibrational state) is larger than expected by analogy with Ar–SiH4, indicative of nearly free internal rotation by the silane monomer unit in Ne–SiH4. The smaller anisotropy of Ne–SiH4 compared with Ar–SiH4 results in a new angular momentum coupling scheme. Transitions arising from 22Ne–SiH4 correlating to SiH4 R(0) have also been observed and fitted; the higher than anticipated intensities demonstrate a novel isotope enrichment effect in the supersonic jet which is discussed. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.471779
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  • 5
    Electronic Resource
    Electronic Resource
    Spectroscopy and structure of the open-shell complex O2–N2O (1997)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 7658-7666 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The high-resolution spectrum of O2–N2O, the first for a complex containing more than one unpaired electron, has been studied in the region of the ν3 N2O monomer vibrational band using a molecular beam diode laser absorption spectrometer. The spectrum has been completely analyzed using a newly developed effective Hamiltonian. The rotational constants are accurately determined for both ground and excited vibrational states. The equilibrium structure of the complex is planar, with a separation between the centers of the mass of two monomers of 3.423 Å. The structural angles have been experimentally determined as: either θO2=58° and θN2O=77°, or θO2=122° and θN2O=100°. The large amplitude motion of the monomers leads to the complex having an effective out-of-plane root mean square angle of φ=φ1−φ2(approximate)23°. In addition, an interpretation of the structure of the complex is given in terms of an intermolecular potential using a model described by Muenter. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.475115
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  • 6
    Electronic Resource
    Electronic Resource
    Spectroscopy and dynamics of rare gas-spherical top complexes. III. The infrared spectrum of the ν3 band of Ne–SiH4 ( j=1←1 and j=2←1 transitions) (1997)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 2738-2751 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The infrared spectrum of the rare gas-spherical top complex Ne–SiH4 has been recorded in a supersonic jet in the region of the SiH4 ν3 triply degenerate stretching vibration at ∼2189 cm−1. The Ne–SiH4 spectrum is complex with no obvious regular band structure; a previous paper has reported the assignment and analysis of bands correlating with the SiH4 R(0) (K=0←0, K=1←0) and P(1) (K=0←0, K=0←1) transitions. This paper concludes the study of Ne–SiH4, with the assignment and analysis of bands correlating with the SiH4 Q(1) (K=0←0, K=1←0, K=0←1, K=1←1) and R(1) (K=0←0, K=1←0, K=1←1, K=2←1) transitions. This was facilitated by a twofold approach: The bands were identified by the use of a theoretical intermolecular potential, with potential parameters determined by reference to the two bands previously fitted; and the relative magnitudes of the Coriolis interactions between the K sublevels within the bands determined by explicit calculation of the Coriolis matrix elements. Having fitted the bands to appropriate energy-level expressions, an effective anisotropic potential for the internal rotation of the SiH4 molecule within the complex was fitted to the total of 15 observed band origins. With a fixed R approximation, the V3 anisotropic term was found to be ∼30 cm−1, approximately one-third that of Ar–SiH4, reflecting the freer rotation of the SiH4 molecule when complexed with the less polarizable Ne atom. However, the overall quality of the fit was an order of magnitude worse than that for Ar–SiH4, indicating increased importance of the radial dependence of the Ne–SiH4 potential compared to that of Ar–SiH4. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.474700
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  • 7
    Electronic Resource
    Electronic Resource
    Theory of rotational energy levels of open-shell complexes containing the O2 molecule (1997)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 7651-7657 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new effective Hamiltonian is presented for the analysis of the high-resolution spectra of open-shell van der Waals complexes containing the O2 molecule. The effects of electron spin are included but the complications of nuclear spin and resultant nuclear spin splitting are neglected. The Hamiltonian is composed of the rotational, centrifugal distortion, and spin–spin interaction terms. The resulting energy levels are divided into two well-separated groups and the pattern is a complicated function of θ (the angle that the O2 molecule makes with the principal a axis of the complex) and φ (the azimuthal angle of the O2 out of the plane defined by the a and b axes of the complex). This model has been successfully applied to analyze the high-resolution spectrum of O2–N2O in the region of the N2O monomer ν3 vibrational band, which will be presented in a separate paper. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.475114
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  • 8
    Electronic Resource
    Electronic Resource
    A high resolution spectroscopic study of the open-shell complex ArNO2 (1996)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 6756-6770 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Microwave and infrared spectra of the open-shell complex ArNO2 have been recorded. The microwave spectrum (6–18 GHz) consisted solely of the a-type transitions 505←404, 404←303, 303←202, and 202←101 involving the Ka=0 state and 523←422, 524←423, 422←321, 423←322, 321←220, 322←221 involving the Ka=2 state. These transitions showed structure due to fine, magnetic hyperfine and electric quadrupole interactions. The infrared spectrum, associated with the ν3 asymmetric vibrational mode of the NO2 monomer, consisted of three bands (RP0, RQ0, and RR0 and both K doublets of PP2, PQ2, and PR2) centered around 1615 cm−1. The data have been fitted to a semirigid Hamiltonian to determine the molecular parameters. The derived parameters are analyzed in terms of those of the free NO2 radical. Changes in these parameters upon complexation can be caused by a geometric effect due to the rotation of the inertial axes from the monomer to the complex, and an electronic effect caused by a distortion of the electronic wave functions on complex formation. The electronic changes (which may give an indication of incipient chemical bond formation) are shown to be very small. The absence of odd Ka″ states in both the infrared and microwave spectra was rationalized in terms of a high frequency tunneling motion of the NO2 within the complex. Both a dynamics calculation and a model potential based on atom–atom interactions provided additional support for a nonplanar equilibrium structure with a low barrier to planarity. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.472998
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  • 9
    Electronic Resource
    Electronic Resource
    Rotational spectra of rare gas-nitric oxide van der Waals molecules. Part 1. Theory of the rotational energy levels (1986)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 90 (1986), S. 3331-3338 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100406a007
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  • 10
    Electronic Resource
    Electronic Resource
    Rotational spectra of rare gas-nitric oxide van der Waals molecules. 2. The structure and spectrum of argon-nitric oxide (1986)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 90 (1986), S. 4961-4969 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100412a019
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