Abstract
An investigation has shown that the 3Π state observed in the 3Π–3Σ transition of the PF molecule deviates from the known triplet formula. By taking into account both the spin–spin interaction and the perturbation of the 3Π state by 1Π states, this anomalous multiplet splitting can be interpreted. From the newly derived equations, accurate values of the rotational constants (B and D) and the multiplet splitting constants (A) have been derived for the ν = 0 and ν = 1 levels of the 3Π state.

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