Superfine and hyperfine structures in the v3 band of 32SF6

Bordé, J.; Bordé, Christian J.

doi:10.1016/0301-0104(82)85047-7

Cited by 65 publications

(17 citation statements)

References 35 publications

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“…The parameters marked by an asterisk were fixed to zero. P (5) gives the value of the parameter obtained by fitting of the 136 lines of paper I with the fifth order Hamiltonian. 1 state Hamiltonian.…”

Section: Table 5 Values Of the 52 Adjusted Parameters Of The Tenth-ormentioning

confidence: 99%

“…In this case, the linewidth was limited by transit and power broadening to a larger value for which the hyperfine structure was not resolved. Furthermore, for tight superfine clusters, the hyperfine mixing of levels with different vibration-rotation symmetry species (5,6) gives rise to complicated asymmetrical structures which are only partly resolved. For a number of these cases we have calculated the expected struc-ture to determine an approximate position of the true vibrationrotation line center (i.e., free of hyperfine effects).…”

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confidence: 99%

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New Accurate Fit of an Extended Set of Saturation Data for the ν3 Band of SF6: Comparison of Hamiltonians in the Spherical and Cubic Tensor Formalisms

Acef

Bordé

Clairon

et al. 2000

Journal of Molecular Spectroscopy

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Section: Table 5 Values Of the 52 Adjusted Parameters Of The Tenth-ormentioning

confidence: 99%

mentioning

confidence: 99%

New Accurate Fit of an Extended Set of Saturation Data for the ν3 Band of SF6: Comparison of Hamiltonians in the Spherical and Cubic Tensor Formalisms

Acef

Bordé

Clairon

et al. 2000

Journal of Molecular Spectroscopy

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“…In the case of an octahedral-type molecule like the SF 6 , we can follow the discussion given in reference [5].…”

Section: Symmetry Considerationsmentioning

confidence: 99%

“…The study of magnetic hyperfine structures F o r P e e r R e v i e w O n l y detected in highly symmetric molecules like this has progressed enormously in the seventh and eighth decades of last century. Some of the fundamental tools for that progress were the ultra-high resolution infrared spectroscopy [1][2][3] and the development of a tensorial formalism suitable for the interpretation of the measured spectra [4][5][6][7][8]. However, the theoretical determination of the electronic contribution to the nuclear hyperfine constants included in the hamiltonian that describes the magnetic hyperfine structures, could not be achieved in those days due to the impossibility of achieving sufficiently accurate calculations.…”

Section: Introductionmentioning

confidence: 99%

Spin-rotation and nuclear shielding constants of sulfur hexafluoride

Palma

Santos

2008

Molecular Physics

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“…It is not a trivial task to work out the relevant Hamiltonian in detail as some account should be taken of the direct vibration-spin coupling because of the vibrational angular momentum. However, as for spherical tops [16], effective spin-rotation constants in the upper level can describe the observed structure of a given rovibrational line. The match between observed and calculated spectra in Fig.…”

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confidence: 97%

Hyperfine lifting of parity degeneracy and the question of inversion in a rigid molecule

1993

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This Letter demonstrates that the parity degeneracy of isolated vibration-rotation states of a rigid molecule can be removed by hyperfine interactions. Hyperfine structures of infrared transitions in PH3 are obtained by saturation spectroscopy around 10 fim. One of these is used to demonstrate unequivocally that degenerate states of opposite parity are separated by the proton hyperfine interactions. We show that alternative explanations involving the physical inversion of the molecule are completely inconsistent with the details of the spectra obtained. In addition to the splitting conclusion, which has very wide generality, new confidence limits are placed on the possible inversion splitting.PACS numbers: 33.20.Ea, 35.20.Jv, 35.20.Sd The degrees of freedom of most molecules in their ground electronic levels can be divided among translations, vibrations, rotations, large amplitude motions, and nuclear spin. Among large amplitude motions inversion plays a peculiar role since parity, the associated quantum number, is always good because of the invariance property of space under inversion in the absence of weak interactions. When a molecule inverts freely it is not surprising to find that the degeneracy of levels of opposite parity is lifted. The first important result of this paper is to show experimentally, via the example of phosphine, that the degeneracy will be lifted even for a rigid molecule in which there is no inversion. We show, further, that this result is intimately connected to the Pauli principle and that there can be no essential degeneracy with parity.Following earlier work on hyperfine effects in ammonia, we will classify the vibration-rotation and hyperfine states of a rigid molecule such as phosphine (PH3) under the geometrical point group C-$ v [1,2] and use the Landau [3] and Berger [4] notations. The rovibrational states are characterized by quantum numbers / and k for total orbital angular momentum and its component along the symmetry axis, respectively, while A^l&l. v is the quantum number for vibrational excitation, and / is the quantum number for the corresponding component of angular momentum along the symmetry axis. Thus, for example, the degenerate V4 state excited to the level 1*4-1 has / = ± 1. Finally, the parity, r =( ± ), completes the description of the rovibrational states. For symmetric top molecules, it is convenient to introduce the symmetric (s) and antisymmetric (a) character of a state upon reflection in a plane perpendicular to the symmetry axis. The correspondence between r and v is r =(+) if v ~(s) and K even or if v=(a) and K odd; otherwise, r^C -). States having k~l -± 3n form a representation A\+Ai except when k ~/=0, the states then being either A\ or A2 depending upon J and r. States having k -I = ± (3n + 1) or ± On 4-2) are of symmetry E. /p, the nuclear spin of 3l P, is j and the corresponding symmetry must necessarily be A\ as the atom is certainly on the symmetry axis. Then, the total proton spin, l\\, must be included. Proton spin states with I\\ = j and /H -...

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Superfine and hyperfine structures in the v3 band of 32SF6

Cited by 65 publications

References 35 publications

New Accurate Fit of an Extended Set of Saturation Data for the ν3 Band of SF6: Comparison of Hamiltonians in the Spherical and Cubic Tensor Formalisms

New Accurate Fit of an Extended Set of Saturation Data for the ν3 Band of SF6: Comparison of Hamiltonians in the Spherical and Cubic Tensor Formalisms

Spin-rotation and nuclear shielding constants of sulfur hexafluoride

Hyperfine lifting of parity degeneracy and the question of inversion in a rigid molecule

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