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Splitting due to tunnelling via the potential energy barrier has played asignificant role in the study of molecular spectra since the early days ofspectroscopy. The observation of the ammonia doublet led to attempts to find aphosphine analogous, but these have so far failed due to its considerablyhigher barrier. Full dimensional, variational nuclear motion calculations areused to predict splittings as a function of excitation energy. Simulatedspectra suggest that such splittings should be observable in the near infraredvia overtones of the $\nu_2$ bending mode starting with $4\nu_2$.

Tunnelling splitting in the phosphine molecule