Inversion–rotation transitions of the fully deuterated hydronium ion, were observed for the first time by microwave spectroscopy. The ion was generated in a hollow cathode cell by dc-glow discharge of a mixture of and Twenty six P- and Q-branch transitions were measured precisely for the lowest pair levels of inversion motion in the frequency region of 220–565 GHz. The ground-state inversion splitting and effective molecular constants for the upper and lower levels were determined by a least-squares fit of the measured line frequencies. The inversion splitting was determined to be 15.355 504 4(45) cm−1, where the number in parentheses denotes three standard deviations of the fit.
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