Internal rotation and hyperfine coupling interaction in deuterated acetaldehyde

Theoretical and experimental investigations of the hyperfine structure of deuterated acetaldehyde (CD3COH) are presented. The theoretical approach accounts for the large amplitude internal rotation of the CD3 group. A hyperfine Hamiltonian, depending on the large amplitude torsional angle, is written taking into account quadrupole hyperfine coupling arising from the three deuterium atoms. Effective hyperfine coupling Hamiltonians are derived for A- and E-type rotation-torsion levels. In the former case, a very symmetrical operator arises in which the hyperfine coupling is the same for all three deuterium atoms. In the latter case the operators are less symmetrical. Hyperfine levels are calculated using symmetry adapted hyperfine wavefunctions in order to build total hyperfine-rotation-torsion wavefunctions satisfying the Pauli exclusion principle. The theoretical approach is used to carry out analyses of six hyperfine patterns which were recorded using a pulsed molecular beam Fourier transform microwave spectrometer. The experimental resolution of this apparatus allows us to resolve individual hyperfine components in many cases. The results of the analysis are consistent with deuterium atoms having an effective quadrupole coupling tensor which, except for appropriate rotations, is quite close to that in CH3D.