Millimeter- and submillimeter-wave length spectrum of the partially deuterated ammonias; A study of inversion, centrifugal distortion, and rotation-inversion interactions

Abstract

Eighty-two new rotation-inversion transitions of the light asymmetric rotors NH2D and ND2H have been measured in the 80–600 GHz region by means of high resolution microwave techniques. Included among these transitions are several submillimeter R-branch transitions which make possible a calculation of both the rotational and distortion parameters which characterize the molecule. An accurate inversion Hamiltonian is developed and used as a preliminary step to a rotation-distortion treatment of the molecule. The spectrum of ND2H reveals the existence of a rotation-vibration interaction which significantly alters the energy of a number of ground vibrational state levels. The results of an analysis technique which incorporates the effects of this perturbation as well as the inversion effects are presented. This procedure makes possible the analysis of all observed transitions to within experimental uncertainties as well as the accurate prediction of unobserved transitions. The rotational constants which result from this work are (MHz): For NH2D, O+ vibrational state,a= 290 286.53 ± 0.21,B= 192 240.15 ± 0.42,C= 140 602.50 ± 0.42; for NH2D, O− vibrational state,a= 290 192.14 ± 0.21,B= 192 176.27 ± 0.42,C= 140 625.64 ± 0.42; for ND2H, O+ vibrational state,a= 223 222.92 ± 0.18,B= 160 433.96 ± 0.17,C= 112 305.40 ± 0.17; for ND2H, O− vibrational state,a= 223 147.21 ± 0.14,B= 160 423.37 ± 0.13,C= 112 313.72 ± 0.13.