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  • 1985-1989  (3)
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  • 1
    Electronic Resource
    Electronic Resource
    Spin–orbit distortion of the hyperfine structure in heavier molecules: Breakdown of the case (aβ) formalism in the B 3Φ–X 3Δ system of gaseous NbN (1989)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1-12 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A detailed analysis of the rotational and hyperfine structure of the (0,0) band of the B 3Φ–X 3Δ electronic transition of NbN has been performed from sub-Doppler spectra taken with linewidths of about 50 MHz. The Nb hyperfine structure is impressively wide in both states, but particularly so in X 3Δ where one of the unpaired electrons occupies a σ orbital derived from the metal 5s orbital. The electron spin and hyperfine structures do not follow the expected case (aβ ) coupling because of extensive second order spin-orbit effects. It is shown that the asymmetry in the spin–orbit structure of X 3Δ is explained almost quantitatively by interaction with a 1 Δ state from the same electron configuration (which lies at 5197 cm−1); also cross terms between the spin–orbit and Fermi contact interactions in the matrix element 〈3Δ2||H||1Δ〉 produce a large correction to the apparent coefficient of the I⋅L magnetic hyperfine interaction in X 3Δ2. The hyperfine structure in a triplet state turns out to be extremely sensitive to the details of the electron spin coupling, and reversals in the sense of the hyperfine structure in the 3Φ4–3Δ3 and 3Φ2–3Δ1 subbands are shown to be consistent with the3Δ state being a regular spin–orbit multiplet (A〉0). Particular care has been taken with the calibration, which has meant that extra terms have needed to be added to the magnetic hyperfine Hamiltonian to account for the spin–orbit distortions: instead of the usual three parameters needed in case (aβ ) coupling, the B 3Φ state has required four parameters and the X 3Δ state has required five. The model explains the data very well, and the standard deviation in the least-squares fit to more than 1000 hyperfine line frequencies was 0.000 58 cm−1 (17 MHz).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.457505
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    A laser-induced fluorescence study of bands of the red system of gaseous CoO: Evidence for a 4Δi ground state (1987)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 5231-5238 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Three bands of the "red'' system of gaseous CoO have been rotationally analyzed using laser-induced fluorescence techniques. The available evidence indicates that the lower levels are the Ω=7/2 and 5/2 spin–orbit components of a 4Δi electronic state, which is assigned as the ground state of the molecule. The cobalt nuclear hyperfine splittings are small in the ground state, which suggests that no unpaired electron in a σ molecular orbital derived from the Co 4s atomic orbital is present, so that the electron configuration is presumably σ2δ3π2; the ground state bond length (r0) is 1.631 A(ring). The upper electronic levels are heavily perturbed, both rotationally and vibrationally, and their hyperfine structures, though following case (a) behavior, are large and irregular. This work on CoO completes the determination of the ground state symmetries and bond lengths for the whole series of the 3d transition metal monoxides; some comparisons for the members of the series are given.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.452599
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    Polarization spectroscopy of Sr79Br and Sr81Br: Analysis of theX 2 Σ + andB 2 Σ + hyperfine structure (1986)
    Springer
    The European physical journal 1 (1986), S. 103-112 
    Details
    ISSN: 1434-6079
    Keywords: 33.40.Hp ; 33.20.Kf ; 35.20.Sd
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Microwave optical polarization spectroscopy has been used to measure the hyperfine structure in theX 2 Σ + (v=0) electronic ground state of Sr79Br and Sr81Br. Optical hyperfine structure in theB 2 Σ +−X 2 Σ + (0,0) system was resolved by Doppler-free laser polarization spectroscopy. The magnetic hyperfine parametersb andc and the electricquadrupole hfs parametereqQ were determined for theX 2 Σ + andB 2 Σ + states of both molecules. The magnetic hfs has been interpreted as an effect of halide electron spin polarization. The electric quadrupole coupling constants are compared with the alkali halides and discussed in terms of Sternheimer antishielding in polar molecules.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01384664
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    Paper (German National Licenses)
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