Publication Abstracts

Thaddeus et al. 1964

Thaddeus, P., L.C. Krisher, and J.H.N. Loubser, 1964: Hyperfine structure in the Microwave spectrum of HDO, HDS, CH2O, and CHDO : Beam-maser spectroscopy on asymmetric-top molecules. J. Chem. Phys., 40, 257-273, doi:10.1063/1.1725107.

Hyperfine structure in the 220→221 rotational transition of HDO at 10 278.2 Mc/sec and HDS at 11 283.8 Mc/sec, and in the 211→212 rotational transition of CH2O at 14 488.6 Mc/sec and CHDO at 16 038.1 Mc/sec, has been investigated with a high-resolution beam maser microwave spectrometer. Linewidths of 5 kc/sec have been obtained. The hyperfine Hamiltonian for an arbitrary number of nuclei with quadrupole, spin-rotation, and spin-spin interactions is discussed, and the matrix elements of the Hamiltonian and the intensities of hyperfine transitions calculated in terms of the tabulated 6j coefficients. Quadrupole and spin-rotation constants and bond lengths which have been determined are, for the 220 state of HDO: (eqJQ)D = 79.3±0.3 kc/sec, CH = -43.47±0.11 kc/sec, CD = -2.33±0.02 kc/sec; for the 221 state of HDO: (eqJQ)D = 79.6±0.3 kc/sec, CH = -43.63±0.13 kc/sec, CD = -2.20±0.02 kc/sec; for the 220 state of HDS: (eqJQ)D = 42.9±0.4 kc/sec, CH = -25.03±0.13 kc/sec, CD = -0.47±0.02 kc/sec; for the 221 state of HDS: (eqJQ)D = 43.3±0.4 kc/sec, CH = -25.45±0.13 kc/sec, CD = -0.22±0.02 kc/sec; for CH2O: CH(211)-CH(212) = 2.26±0.13 kc/sec, CH(211) = 0.65±0.50 kc/sec, ⟨1/rHH3-1/s = 1.898±0.017 Å; for CHDO: (eVξξQ)D = 170.0±2.0 kc/sec (where ξξV is the second derivative of the electrostatic potential along the CD bond), CH(211)-CH(212) = 2.42±0.50 kc/sec, CD(211)-CD(212) = 0.25±0.10 kc/sec, CH(211) = 0.2±1.0 kc/sec, CD(211) = 0.13±0.20 kc/sec, and ⟨1/rHD3-1/3 = 1.88±0.10 Å. The V calculated from the deuteron quadrupole coupling constants are, for HDO: 1.56×1015 statvolt/cm2; for HDS: 0.76×1015 statvolt/cm2; and for CHDO: 0.83×1015 statvolt/cm2.

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BibTeX Citation

@article{th05100g,
  author={Thaddeus, P. and Krisher, L. C. and Loubser, J. H. N.},
  title={Hyperfine structure in the Microwave spectrum of HDO, HDS, CH2O, and CHDO : Beam-maser spectroscopy on asymmetric-top molecules},
  year={1964},
  journal={J. Chem. Phys.},
  volume={40},
  pages={257--273},
  doi={10.1063/1.1725107},
}

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RIS Citation

TY  - JOUR
ID  - th05100g
AU  - Thaddeus, P.
AU  - Krisher, L. C.
AU  - Loubser, J. H. N.
PY  - 1964
TI  - Hyperfine structure in the Microwave spectrum of HDO, HDS, CH2O, and CHDO : Beam-maser spectroscopy on asymmetric-top molecules
JA  - J. Chem. Phys.
VL  - 40
SP  - 257
EP  - 273
DO  - 10.1063/1.1725107
ER  -

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