MODELLING OF ROTATION-VIBRATION DYNAMICS IN $Ar-CO_{2}$ AND HCN

Author Institution: Department of Chemistry, Harvard UniversityThe Born-Oppenheimer angular-radial separation method (BOARS) for calculating rotation-vibration states of atom-diatomic complexes has been applied to $Ar-CO_{2}$ and HCN. The analysis of the molecular beam electric resonance data for $Ar-CO_{2}$ included the calculation of both excited J and K rotational levels of the complex as well as the K-doublet splitting for various values of K. The potential energy surface which best fits the experimental measurements will be compared with previously published \emph{ab initio} surfaces. The dynamics of highly excited bending states in HCN were explored using the BOARS method by treating CN as a rigid diatomic. The effect on the vibrational levels of Coriolis coupling, tunnelling to HNC, and internal ``free rotor” states are examined, in light of their impact on overall level densities