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  • Access by Xinjiang University

Large Electronic Isotope Effects in Molecular Spectra

Herrick L. Johnston*

  • Department of Chemistry, Ohio State University

  • *Fellow of the John Simon Guggenheim Memorial Foundation and in residence in the II Physical Institute, Göttingen, Germany, while this material was prepared.

Phys. Rev. 45, 79 – Published 15 January, 1934

DOI: https://doi.org/10.1103/PhysRev.45.79

Abstract

The large electronic isotope effect in the spin coupling of II2-terms, reported by Johnston and Dawson for boron monoxide and for the heads of the OH2 bands is confirmed by measurements of the fine line structure in the isotopic OH bands. Both for BO and for OH the observed increase in the doublet spacings, in the molecule with the heavier isotope, agrees closely with the results to be expected from Hill and Van Vleck's theoretical treatment of spin coupling energy, although their equations do not so well reproduce the separate doublets. This isotope effect is zero at the band origins, increases to a maximum (which amounts to 20 cm1 in the 0″ vibrational level of OH) and approaches zero asymptotically at high rotational quantum numbers. A large electronic isotope effect in Λ-doubling is also observed for OH. This effect, which is zero at the band origin and increases with increasing rotation, amounts to 17 cm1 at K=25. It is not correctly accounted for by Van Vleck's equations for Λ-doubling although ratios of the Λ-doublets in OH1 and OH2 are correctly given, for a case b molecule. No noticeable effect was observed on the spacings of the Σ2-doublets in the excited state of OH.

References (7)

  1. Johnston and Dawson, Naturwiss. 21, 495 (1933)
  2. Unpublished work of Johnston and Dawson
  3. Jenkins and McKellar, Phys. Rev. 42, 464 (1932)
  4. Omitted endnote

  5. Dawson and Johnston, Phys. Rev. 43, 980 (1933)
  6. Hill and Van Vleck, Phys. Rev. 32, 250 (1928)
  7. Van Vleck, Phys. Rev. 33, 467 (1929)

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