Globally Accurate Full-Dimensional Potential Energy Surface for H2 + HCl Inelastic Scattering.

Abstract

A globally accurate full-dimensional potential energy surface (PES) for the inelastic scattering between H2 and HCl is developed on the basis of a large number of points calculated at the coupled-cluster singles, doubles, and perturbative triples level of theory. The machine-learned PES is trained with 42 417 ab initio points using the permutation invariant polynomial-neural network method, resulting in a root-mean-square fitting error of 5.6 cm-1. Both full- and reduced-dimensional quantum calculations for rotationally inelastic scattering are performed on this new PES and good agreement is obtained with previous quantum dynamical results on a reduced-dimensional model. Furthermore, strong resonances are identified at collision energies below 100 K, including cold conditions. This new PES provides a reliable platform for future studies of scattering dynamics with vibrationally excited collision partners in a wide range of collision energies extending to cold and ultracold conditions.