Intensities in Molecular Electronic Spectra X. Calculations on Mixed‐Halogen, Hydrogen Halide, Alkyl Halide, and Hydroxyl Spectra

TLDR: In this article, the dipole strengths for certain perpendicular-type transitions N→Q in the mixed halogens, the hydrogen and monovalent metal halides, and the alkyl halides are calculated theoretically by the LCAO and by the AO approximations.

Abstract: The dipole strengths for certain perpendicular‐type transitions N→Q in the mixed halogens, the hydrogen and monovalent metal halides, and the alkyl halides, are calculated theoretically by the LCAO and by the AO approximations. The scanty experimental absorption coefficient data on these halides (particularly the hydrogen and alkyl bromides and iodides) are critically examined, and acceptable experimental dipole strengths are obtained for the bromides. These show, very gratifyingly, the same kind of agreement with the calculated values as was found in IX of this series for the N→Q transitions in F2, Cl2, and Br2. The iodides, however, just like I2, show anomalously low strengths for the true N→Q part of the intensity (N→3II1 and N→1II), together with high strength for N→3II0+. These anomalies are ascribed here, as in I2, to partial case c coupling (partial preservation of atomic J's). The comparison between theory and experiment confirms the interpretation of the ultraviolet continua of the hydrogen and a...