Centrifugal distortion analysis of the rotational spectrum of aziridine: Comparison of different Hamiltonians

Previous measurements of rotational spectrum of aziridine up to 1.85 THz have been supplemented by new data in 225-660 GHz frequency range. A total of 1465 transitions (915 of them are newly assigned ones) with maximum values of J = 59 and K_c = 50 were fit to a standard Watson Hamiltonian using the S- and A-reductions and the representations I^r and III^r. Although aziridine 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). It is explained that the failure of the combination (A, III^r) is due to the large value of the parameter σ=(2C-A-B)/(A-B) which makes some sextic centrifugal distortion constants much too large impeding the convergence of the Hamiltonian. It is also shown that the calculation of the centrifugal distortion constants from a force field is sometimes an ill-conditioned operation. Finally, the use of a non-reduced Hamiltonian (with six quartic centrifugal distortion constants) was successful in the particular case thanks to the method of predicate observations.