The HPO molecule was identified by its microwave spectrum in the reaction of PH3 with microwave discharge products of an H2/O2 mixture; the a‐type R branch transitions of J=1 ← 0 up to 4 ← 3 were observed in the frequency region of 40 to 162 GHz. High‐ K lines showed small splittings due to the phosphorus nuclear spin‐rotation interaction. In addition to the rotational and centrifugal distortion constants, the observed spectrum yielded the nuclear spin‐rotation tensor, the aa component which is −1.12 (37) MHz with 2.5 standard errors in parentheses. This large interaction is discussed in terms of second‐order perturbation theory.

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