Beyond ro-vibrational separation

Abstract

Results are presented for nuclear motion calculations on D⁺₃, H₂D⁺ and the van der Waals complex ArCO in rotationally excited states. These calculations are performed using a two-step variational procedure which allows large ro-vibrational interactions (Coriolis couplings) to be treated accurately. The difficulty of assigning states in systems such as H₂D⁺ where the Coriolis interactions are large is illustrated and the limitations of effective Hamiltonians derived from perturbation theory discussed.