Variational EKE-calculations of rovibrational energies of the ozone molecule from an empirical potential function

We report rovibrational calculations from an empirical potential energy sur face (PES) of the electronic ground state of ozone, using an Exact Kinetic Energy (EKE) operator. The PES was optimised using the EKE Hamiltonian and experimental spectroscopic high-resolution data. The RMS deviation of calcu lations for all experimental band centres directly observed so far in high- resolution spectra is 0.12 cm(-1). The RMS deviation of calculations of rot ational energies up to J less than or equal to 5 is 0.002 cm(-1) for the (0 00) level and 0.015 cm(-1) for five lowest vibrational states. Both rotatio nal and vibrational calculations are cm more accurate than presently availa ble EKE-calculations for O-3. The PES shows a physically meaningful long-ra nge behaviour at the dissociation limit. (C) 2000 Elsevier Science B.V. All rights reserved.