Ab initio studies on complexes of ozone with diatomic molecules

Abstract Møller-Plesset MP2 and coupled cluster CCSD(T) calculations using the aug-cc-pVQZ basis set were performed on structures, energies and harmonic vibrational frequencies of the complexes O3-HF, O3-HCl, O3-OH, O3-H2, O3-N2, O3-CO, O3-O2, O3-F2, O3-Cl2 and O3-FCl. Most complexes have Cs symmetry, with the symmetry plane being the plane of ozone (for the hydrogen bonded O3-HF to O3-OH complexes) or the plane perpendicular to ozone (for most others). Dissociation energies De range from 718 cm-1 to 1137 cm-1 for the hydrogen bonded complexes O3-HCl to O3-HF, and from 200 cm-1 to 477 cm-1 for non-hydrogen bonded complexes from O3-H2 to O3-Cl2. Due to complex formation harmonic vibrational frequencies of the diatomic molecules are red shifted in the hydrogen bonded complexes, from 39 cm-1 for O3-OH to 156 cm-1 for O3-HF. Corresponding infrared intensities increase by a factor of about five.