Choice of the reduction and of the representation in centrifugal distortion analysis: A case study of dimethylsulfoxide

The millimeter-wave and submillimeter-wave spectra of dimethylsulfoxide have been measured up to 660 GHz, corresponding to maximum values of J = 70 and K_c = 68. A total of 3331 transitions (corresponding to 2133 distinct frequencies) were fit to a standard Watson Hamiltonian using the S- and A-reductions and the representations I^r and III^r. Although dimethylsulfoxide is an asymmetric oblate top, the combination (A, III^r) gives the worst results. From the point of view of the convergence of the Hamiltonian, the best results are obtained with the combination (S, III^r) but the least-squares system of normal equations is better conditioned with representation I^r. These results are compared to those obtained for a few typical molecules.