Molecular Rydberg transitions. I. Low-energy Rydberg transitions in methyl halides

The energies of the rare gas transitions p6; 1S → (p5; 2PJ) nl; Γ, where p is the highest occupied p AO of the ground configuration and nl is the nth virtual l AO, exhibit a significant linear correlation, for fixed n and l, with the ionization energies p6; 1S → p5; 2PJ. Similar correlations exist for Rydberg transitions in CH3X molecules, X = Cl, Br, I. The assignment capability of the combined interatomic and intermolecular correlations is equivalent, at least in the case of the methyl halides, to that of the Rydberg equation for n ? 5.