On neglecting Coriolis and related couplings in first-principles rovibrational spectroscopy: considerations of symmetry, accuracy, and simplicity

Abstract

The rotation-vibration (Coriolis) coupling contribution to variationally computed rovibrational energy levels is investigated, employing triatomic AB2 molecules as models. In particular, calculations are performed for H216O, across a range of vibrational and rotational excitations, both with and without the Coriolis contribution. A variety of different embedding choices are considered, together with a hierarchy of increasingly severe approximations culminating in a generalized version of the so-called “centrifugal sudden” method. Several surprising and remarkable conclusions are found, including that the Eckart embedding is not the best embedding choice.