We have observed microwave transitions in the HD+ and D2 + ions involving energy levels very close to their dissociation limits. In HD+ the spectrum detected arises from a rotational transition between the two highest bound vibration-rotation levels in the 1sσ ground state, whilst in D2 + we have detected electronic transitions between high-lying vibration-rotation levels of the ground 1sσg electronic state and the 2pσu long-range van der Waals state.
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Carrington et al. (1989) studied this question.
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