An accurate 5D potential energy surface for H3O+-H2interaction

Abstract

Modeling of the observational spectra of H3O+ allows for a detailed understanding of the interstellar oxygen chemistry. While its spectroscopy was intensively studied earlier, our knowledge about the collision of H3O+ with the abundant colliders in the interstellar medium is rather limited. In order to treat these collisional excitation processes, it is first necessary to calculate the potential energy surface (PES) of the interacting species. We have computed the five-dimensional rigid-rotor PES of the H3O+-H2 system from the explicitly correlated coupled-cluster theory at the level of singles and doubles with perturbative corrections for triple excitations [CCSD(T)-F12] with the moderate-size augmented correlation-consistent valence triple zeta (aug-cc-pVTZ) basis set. The well depth of the PES is found to be rather large, about 1887.2 cm-1. The ab initio potential was fitted over an angular expansion in order to effectively use it in quantum scattering codes. As a first application, we computed dissociation energies for the different nuclear spin isomers of the H3O+-H2 complex.