Accurate ab initio near-equilibrium potential energy and dipole moment functions of the ground electronic state of ozone

Abstract

We report a highly correlated multireference configuration interaction calculation of the near-equilibrium potential energy surface of ozone using a large correlation consistent basis set. Three-dimensional analytical expressions are obtained for the potential energy and dipole moment functions using least-squares fits to ab initio points near the C2v equilibrium geometry. Low-lying vibrational band origins of O316 and some of its isotopic variants are calculated using the ab initio potential energy function. The calculated fundamental frequencies for the symmetric stretching and bending vibrations are within about 3 cm−1 of the observed values, while that for the antisymmetric stretch deviates from experiment by about 13 cm−1. The agreement with experiment can be significantly improved if the ab initio potential energy function is scaled in the antisymmetric stretching coordinate. Absolute infrared absorption intensities are also calculated using ab initio electric dipole moment functions and in good agreement with the available experimental data.