The transition-state region of the O(3P)+O2(3Σg-) potential energy surface

New electronic structure calculations for the transition-state region of the lowest ozone potential energy surface are reported. A two-dimensional potential energy surface in the asymptotic channel is calculated with the O-2 bond distance being fixed. The calculations are performed at the multireference average quadratic coupled cluster level of theory using full-valence complete active space self-consistent field wave functions and the augmented correlation consistent polarized V6Z atomic basis set. The general shape of the potential energy surface as predicted in earlier studies, that is, a narrow transition state below the O+O-2 asymptote, is confirmed by the present calculations. The transition state is 181 cm(-1) below the asymptote and 72 cm(-1) above the van der Waals-like minimum. The changes in the O+O-2-->O-3* capture cross section and rate constant when the new potential energy surface is employed are investigated by means of classical trajectory calculations. (C) 2004 American Institute of Physics.