Rotation—Vibration Interaction and Other Corrections to the Spin Doublet Separation in 2Π Diatomic Molecules

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Abstract
The effect of rotation—vibration interaction on the spin doublet separation in 2Π states of diatomic molecules is treated. Almy and Horsfall's refinement of Hill and Van Vleck's treatment is questioned and an alternative approach making use of Dunham's treatment of 1Σ diatomic molecules is used. The J dependence of the spin‐orbit coupling constants is included in the discussion. Vibrational wavefunctions (including rotation—vibration interaction) and matrix elements are discussed. Additional corrections arising from the Λ doubling and from the spin—rotation interaction ΓN·S are briefly considered. A comparison of the results of this work with experimental spin doublet separation leads to better agreement between theory and experiment for the examples treated.