Ab initio studies on complexes of ozone with diatomic molecules

Abstract

Coupled cluster CCSD(T) calculations using the aug-cc-pVQZ basis set were performed on structures and energies of the complexes O3-HF, O3-HCl, O3-OH, O3-H2, O3-N2, O3-CO, O3-O2, O3-F2, O3-Cl2, and O3-ClF. Most complexes have Cs symmetry, with the symmetry plane being the plane of ozone (for hydrogen bonded O3-HF to O3-OH and for halogen bonded O3-Cl2 and O3-ClF) or the plane perpendicular to ozone (for most others). Dissociation energies De range from 718 to 1137 cm−1 for the hydrogen bonded O3-HCl to O3-HF complexes, from 540 to 872 cm−1 for the halogen bonded O3-Cl2 and O3-ClF complexes, and from to 200 to 433 cm−1 for complexes from O3-H2 to O3-CO. In hydrogen-bonded complexes calculated harmonic vibrational frequencies of the diatomic molecule are red shifted, by 164 cm−1 for O3-HF and by 52 cm−1 for O3-HCl, combined with blue shifts up to 29 cm−1 for the ozone frequencies. In halogen-bonded complexes, the halogen frequencies of O3-ClF are red shifted by up to 13 cm−1.