Full-Dimensional Quantum Dynamics Studies of Ro-vibrationally Inelastic Scattering of H2O with Ar: A Benchmark Test of the Rigid-Rotor Approximation

Abstract

While the rigid-rotor (RR) approximation is usually considered to be accurate for describing pure rotationally inelastic scattering involving diatoms in their ground or low-lying vibrational states, its validity in scattering involving polyatomic molecules has not been fully examined. The existence of soft/anharmonic vibrational modes in polyatomic molecules could make rotational-vibrational energy transfer rather efficient, thus undermining the premise of the RR approximation. In this work, we conduct a benchmark test of the RR approximation in the rotationally inelastic scattering of the H2O(v2 = 0, 1) + Ar system by comparing with full-dimensional quantum scattering calculations. We demonstrate that the error in the RR rate coefficient for v2 = 0 is less than 5%, while it can reach up to 20% for some initial states within the v2 = 1 manifold. These results indicate that the RR approximation gradually deteriorates with increasing quantum number v2. Vibrational relaxation dynamics of this system was also studied, and it is found that transitions from initial states with a large rotational quantum number of projection on the a principal axis are more efficient. These results shed valuable light on ro-vibrationally inelastic scattering involving polyatomic molecules.