On the use of nonrigid-molecular symmetry in nuclear motion computations employing a discrete variable representation: A case study of the bending energy levels of CH5.

Abstract

A discrete-variable-representation-based symmetry adaptation algorithm is presented and implemented in the fourth-age quantum-chemical rotational-vibrational code GENIUSH. The utility of the symmetry-adapted version of GENIUSH is demonstrated by the computation of seven-dimensional bend-only vibrational and rovibrational eigenstates of the highly fluxionally symmetric CH5+ molecular ion, a prototypical astructural system. While the numerical results obtained and the symmetry labels of the computed rovibrational states of CH5+ are of considerable utility by themselves, it must also be noted that the present study confirms that the nearly unconstrained motion of the five hydrogen atoms orbiting around the central carbon atom results in highly complex rotational-vibrational quantum dynamics and renders the understanding of the high-resolution spectra of CH5+ extremely challenging.