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The fine structure theory of4Π states in diatomic molecules is reconsidered from the point of view of exact numerical diagonalization of the four-by-four perturbation matrix. The interaction with other electronic states is accounted for through a second order Van Vleck transformation. Centrifugal distortion corrections are also added to the matrix elements, and a new spin-spin matrix element of the type ΔΛ = -ΔΣ = ±2 is in particular found to contribute to the Λ-doubling. The theoretical results are applied to thea4Πustate in O2+and theB4Π state in VO.
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L. Veseth (1975) studied this question.
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