Microwave spectrum of PHD: hyperfine structure

The rotational spectrum of the monodeuterated PH₂ radical was studied using a source-modulated submillimeter-wave spectrometer. The PHD radical was generated in a free space absorption cell by a dc-glow discharge in a gas mixture of PH₃ and D₂. Six a-type and 20 b-type rotational transitions were observed in the frequency region of 170-670 GHz. Hyperfine structure due to the deuterium nucleus was resolved only in the rotational transitions of 1₁₁-0₀₀ and 1₁₀-1₀₁ and in the low F₂ components of N=2-1 transitions. A total of 219 spectral lines were measured of which 145 were analyzed by least-squares methods. These yielded 34 precise molecular constants including the hyperfine coupling constants of phosphorus, hydrogen, and deuterium. The principal axes and principal values of the magnetic dipole coupling tensors of hydrogen in PH₂ and deuterium in PD₂ were derived from the observed values of PHD, PH₂ and PD₂. The principal axis of the hydrogen magnetic dipole coupling tensor in PH₂ makes an angle of 2.29° with the PH bond and its T_σ and T_⊥ principal values are determined to be 12.93 and −18.39 MHz, respectively.