Vibrational and Vibronic Structure in the Valence Electron Spectra of CH3X Molecules (X=F, Cl, Br, I, OH)

Abstract
Valence electron spectra of the methyl halides and of methyl alcohol have been induced by means of the HeI resonance radiation at 21.22 eV. A large number of new vibrational bands are reported. The observation of these was facilitated by a high instrumental resolving power and fast data acquisition. In most cases the new bands are observed in 1 A 12 E transitions but also the electron band of the 1 A 12 A 1 transition of CH3I exhibits extensive progressions of closely spaced vibrational bands not previously reported. The vibrational structure of the 1 A 12 E transitions is affected by vibronic coupling. The structure of the 2e electron band of CH3Cl probably reflects the operation of the Ham effect. Calculations of the band structure including spin-orbit coupling are performed according to a model which is briefly described.

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