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  • Access by Xinjiang University

l-Type Doubling in Linear Polyatomic Molecules

G. Herzberg

G. Herzberg

  • Department of Physics, University of Saskatchewan, Saskatoon, Saskatchewan, Canada

Rev. Mod. Phys. 14, 219 – Published 1 April, 1942

DOI: https://doi.org/10.1103/RevModPhys.14.219

Abstract

The infra-red spectra of C2H2, HCN, and CO2 give evidence of a splitting of the II vibrational levels (in which a ⊥ vibration is singly excited) into two components which is entirely analogous to the Λ-type doubling of the electronic states of diatomic molecules and is called here l-type doubling. The experimental data show that this l-type doubling may be represented by Δν=qiJ(J+1) and that the constant qi is of the same order as the constant αi in B[v]=BeΣαi(vi+12di). The existence of the l-type doubling also explains the apparent discrepancy that the fundamental bands of HCN and C2H2 do not show a convergence of the P and R branches while the Q branch is distinctly shaded to shorter wave-lengths. A preliminary theoretical treatment of the l-type doubling is also given. The doubling is due mainly to the fact that in the displaced position of a perpendicular vibration a linear molecule is a slightly asymmetric top, but to some extent also to the Coriolis interaction of different vibrations. The observed values of qi are all larger than the calculated ones. Taking the l-type doubling into account the rotational constants αi of CO2 have been newly evaluated and from them and the value B000=0.38950 cm1 the rotational constant Be in the equilibrium position is found to be 0.3906±0.0002 cm1 which gives for the moment of inertia Ie=71.61·1040 g cm2 and for the CO distance re=1.1615·108 cm.

References (12)

  1. R. S. Mulliken, J. Phys. Chem. 41, 159 (1937)
  2. D. M. Dennison, Rev. Mod. Phys. 12, 175 (1940)
  3. W. H. Shaffer and A. H. Nielsen, J. Chem. Phys. 9, 847 (1941)
  4. G. W. Funke and G. Herzberg, Phys. Rev. 49, 100 (1936) G. W. Funke, Zeits. f. Physik 99, 341 (1936) ibid.104, 169 (1936)
  5. G. W. Funke and E. Lindholm, Zeits. f. Physik 106, 518 (1937)
  6. A. Levin and C. F. Meyer, J. Opt. Soc. Am. 16, 137 (1928)
  7. Omitted endnote

  8. E. Lindholm, Zeits. f. Physik 108, 454 (1938)
  9. P. F. Bartunek and E. F. Barker, Phys. Rev. 48, 516 (1935)
  10. A. Adel and D. M. Dennison, Phys. Rev. 43, 716 (1933)
  11. J. H. Van Vleck, Phys. Rev. 33, 467 (1929)
  12. S. C. Wang, Phys. Rev. 34, 243 (1929)

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