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The Band Spectrum of Sulphur Monoxide

Emmett V. Martin

  • University of California, Berkeley, California

Phys. Rev. 41, 167 – Published 15 July, 1932

DOI: https://doi.org/10.1103/PhysRev.41.167

Abstract

The spectrum of SO, which lies in the region 2400-4000A, has been photographed in the 2nd order of a 21-foot grating. The wave-numbers of the lines of the seven bands, (0,4), (0,5), (0,6), (0,7), (0,8), (0,9), and (1,4), are tabulated.

Rotational structure.—The analysis of the rotational structure leads to the assignment of the band system to a Σ3, Σ3 electronic transition, and yields the following values of the constants:

Spin fine-structure. The triplets are resolved for K>30 and for K<13. However, due to overlapping of the different branches, the resolution for K<13 could be observed well in the (0,8) band only. It was found that, in order to represent adequately the observed separations of the triplets, it was necessary to modify somewhat the equations in Kramers' theory of spin tripling in Σ3 states. The equations which best respresent the data are: Δ21=AB(2K+3)(γγ)(K+1) Δ23=A+B(2K1)+(γγ)K where, for the (0,8) band, A=2.11, B=10.83, and (γγ)=+0.0150. Of these three constants, A is the only one which is different for different bands; it ranges from -1.97 for the (0,4) band to -2.19 for the (0.9) band. We cannot determine which one, if either, of the two terms, A and B, represents the value of 3(εε) in Kramers' theory. The values of Δ2F1(K) and Δ2F3(K) indicate that γ+0.017 and that γ0.003.

Predissociation and perturbations. Bands with v=0, 1, 2, and 3 are observed to break off at K=66, 53, 39, and 6, respectively. No bands with v>3 are observed. This effect is explained as predissociation, and is assumed to be caused by a I3I state. Not only do the rotational levels for different v end at different values of K, but also the term value at which the break occurs decreases with increasing v. If the potential energy curve for the Π3 state is assumed to have a shallow minimum, a satisfactory explanation of the effect of rotation on predissociation is obtained by an application of Oldenberg's theory of dissociation by rotation. A further indication that the Π3 potential energy curve has a shallow minimum is given by the observed perturbations of the rotational levels of the upper Σ3 state. According to our interpretation, the term value at which the rotational levels for v=3 terminate corresponds to dissociation of the normal state of the SO molecule. The energy of dissociation of this state, measured from the v=0 vibrational level, is calculated to be 5.053±0.001 volts.

Vibrational structure. The origins of several bands of the v=0 progression are calculated, and the vibrational constants of the lower state determined from them. Since the bands with v>1 are too much perturbed to permit an analysis of their rotational structure, it was necessary to use measurements of band heads to determine the vibrational constants of the upper state. The constants obtained are: ωe=1123.73±0.24 cm1, xeωe=6.116±0.017 cm1, ωe=628.7 cm1, and xeωe=5.65 cm1.

References (33)

  1. Frances Lowater, Ast. Jour. 23, 324 (1906)
  2. R. C. Johnson and W. H. B. Cameron, Proc. Roy. Soc. A106, 195 (1924)
  3. V. Henri and F. Wolff, Jour. Phys. Rad. 10, 81 (1929)
  4. R. S. Mulliken, Phys. Rev. 36, 611 (1930)
  5. W. Weizel, Handbuch der Experimentalphysik, Ergänzungswerk, Band I, (1931) A.E Ruark and H. C. Urey, Atoms, Molecules, and Quanta (1930)
  6. A. Kratzer, Zeits. f. Physik 3, 289 (1920)
  7. R. T. Birge, Unpublished work
  8. W. Ossenbrüggen, Zeits. f. Physik 49, 167 (1928)
  9. W. Lochte-Holtgreven and G. H. Dieke, Ann. d. Physik 3, 937 (1929)
  10. S. M. Naude and A. Christy, Phys. Rev. 37, 490 (1931)
  11. S. M. NaudeA. ChristyTransactions of the International Astronomical Union, Vol. III, (1929)
  12. S. M. NaudeA. ChristyPublications of the Allegheny Observatory of the University of Pittsburgh, Vol. VI (1929)
  13. R. S. Mulliken, Rev. Mod. Phys. 2, 105 (1931)
  14. H. A. Kramers, Zeits. f. Physik 53, 422 (1929)
  15. Omitted endnote

  16. Omitted endnote

  17. Kramers' [14] Lochte-Holtgreven and Dieke [9]
  18. Omitted endnote

  19. R. T. Birge and H. H. Nielsen, unpublished work
  20. R. S. Mulliken, Rev. Mod. Phys. 2, 105 (1930) J. H. Van Vleck, Phys. Rev. 33, 467 (1929)
  21. G. Herzberg, Nature 126, 239 (1930)
  22. K. F. Bonhoeffer and L. Farkas, Zeits. f. Physik Chem. (A)134, 337 (1927)
  23. R. de L. Kronig, Zeits. f. Physik 50, 347 (1928) ibid.62, 300 (1930)
  24. G. Herzberg, Erg. exakt. Naturwiss. 10, 207 (1931)
  25. V. Henri, Jour. Phys. Rad. 3, 181 (1922) V. HenriStructure of Molecules (1925)
  26. Omitted endnote

  27. R. T. Birge, Nat'l. Research Council Bulletin on Molecular Spectra, (1926)
  28. R. Frerichs, Phys. Rev. 36, 398 (1930)
  29. A. Christy and S. M. Naudé, Phys. Rev. 37, 903 (1931)
  30. P. M. Morse, Phys. Rev. 34, 57 (1929)
  31. R. de L. Kronig, Band Spectra and Molecular Structure (Cambridge), (1930) R. S. Mulliken, Rev. Mod. Phys. 4, 1 (1932) E. Wigner and E. E. Witmer, Zeits. f. Physik 51, 859 (1928)
  32. O. Oldenberg, Zeits. f. Physik 56, 563 (1929)
  33. W. G. Brown, Phys. Rev. 38, 709 (1931)

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