Torsion—rotation interactions in monodeuterated acetaldehyde

This paper presents an analysis of previously observed rotational transitions up to J = 17 of the sym and asym rotamers of monodeuterated acetaldehyde using a three-level Hamiltonian incorporating connections between rotational states of the vsym = 0, vasym = 0+ and vasym = 0 − torsional energy level manifolds. Rotational transitions observed to be significantly perturbed in earlier studies, where the spectrum was fitted using a single-level Hamiltonian for the vsym = 0 torsional state and a separate two-level Hamiltonian for the non-rigid asym states, are now fitted satisfactorily. It is confirmed that the perturbations detected in the earlier studies and tentatively attributed there to torsion-rotation interactions between the energetically distinct sym and asym manifolds do indeed arise as a consequence of such interactions. Rotational and quartic centrifugal distortion constants are given for each torsional state, together with torsion-rotation coupling constants primarily responsible for the perturba...