DOI: 10.1063/1.1677553. Radiofrequency and Microwave Spectrum of the Hydrogen Fluoride Dimer; a Nonrigid Molecule

Radiofrequency and Microwave Spectrum of the Hydrogen Fluoride Dimer; a Nonrigid Molecule

10.1063/1.1677553

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The radiofrequency and microwave spectra of the K=0 states of (HF)2, (DF)2, and HFDF have been studied by the molecular beam electric resonance method. A unique hydrogen tunnelling motion involving the breaking and reforming of the hydrogen bond causes a splitting of rotational energy levels for (HF)2 and (DF)2, but not for HFDF. The electric dipole selection rules and nuclear spin statistics for the tunnelling molecules have been derived from a consideration of an extended permutation-inversion group. Rotational constants, tunneling doublings, electric dipole moments, and deuterium quadrupole coupling constants have been determined from the observed spectra of the K=0 states. (HF)2(DF)2HFDF(B+C)/2 (MHz)6504.8±2.06252.194±0.0026500.1±0.1ν (MHz)19 776±121579.877 ±0.004μa (D)2.987±0.0032.9919±0.00063.029±0.003(eqQ)Da (KHz)···110±8270±30These results are interpreted with a semirigid, nonlinear model of the dimer geometry. The F—F distance is 2.79 ± 0.05 Å, and the end hydrogen fluoride unit is bent from 60 to 70° from the F—F axis. Large amplitude motion of the hydrogen and deuterium atoms occurs. Higher hydrogen fluoride polymers have been studied by mass spectroscopy and electric deflection methods. All were observed to be nonpolar which is interpreted to imply cyclic structures.

Bibliography

Dyke, T. R., Howard, B. J., & Klemperer, W. (1972). Radiofrequency and Microwave Spectrum of the Hydrogen Fluoride Dimer; a Nonrigid Molecule. The Journal of Chemical Physics, 56(5), 2442â2454.

Authors 3

Thomas R. Dyke (first)
Brian J. Howard (additional)
William Klemperer (additional)

References 36 Referenced 535

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Dates

Type	When
Created	21 years, 6 months ago (Feb. 6, 2004, 3:25 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 4:35 a.m.)
Indexed	2 months, 1 week ago (June 10, 2025, 12:31 a.m.)
Issued	53 years, 5 months ago (March 1, 1972)
Published	53 years, 5 months ago (March 1, 1972)
Published Print	53 years, 5 months ago (March 1, 1972)

Funders 0

None

BibTeX

@article{Dyke_1972, title={Radiofrequency and Microwave Spectrum of the Hydrogen Fluoride Dimer; a Nonrigid Molecule}, volume={56}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1677553}, DOI={10.1063/1.1677553}, number={5}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Dyke, Thomas R. and Howard, Brian J. and Klemperer, William}, year={1972}, month=mar, pages={2442–2454} }

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  "abstract": "<jats:p>The radiofrequency and microwave spectra of the K=0 states of (HF)2, (DF)2, and HFDF have been studied by the molecular beam electric resonance method. A unique hydrogen tunnelling motion involving the breaking and reforming of the hydrogen bond causes a splitting of rotational energy levels for (HF)2 and (DF)2, but not for HFDF. The electric dipole selection rules and nuclear spin statistics for the tunnelling molecules have been derived from a consideration of an extended permutation-inversion group. Rotational constants, tunneling doublings, electric dipole moments, and deuterium quadrupole coupling constants have been determined from the observed spectra of the K=0 states. (HF)2(DF)2HFDF(B+C)/2\u2009(MHz)6504.8\u00b12.06252.194\u00b10.0026500.1\u00b10.1\u03bd\u2009(MHz)19\u2009776\u00b1121579.877 \u00b10.004\u03bca \u2009(D)2.987\u00b10.0032.9919\u00b10.00063.029\u00b10.003(eqQ)Da\u2009(KHz)\u00b7\u00b7\u00b7110\u00b18270\u00b130These results are interpreted with a semirigid, nonlinear model of the dimer geometry. The F\u2014F distance is 2.79 \u00b1 0.05\u2009\u00c5, and the end hydrogen fluoride unit is bent from 60 to 70\u00b0 from the F\u2014F axis. Large amplitude motion of the hydrogen and deuterium atoms occurs. Higher hydrogen fluoride polymers have been studied by mass spectroscopy and electric deflection methods. All were observed to be nonpolar which is interpreted to imply cyclic structures.</jats:p>",
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