Analytical representation for the ozone electronic ground state potential function in the spectroscopically accessible range and extended vibration predictions

Vladimir G. Tyuterev (1) , Roman V. Kochanov (2) , Sergei A. Tashkun (2)

1 GSMA - Groupe de spectrométrie moléculaire et atmosphérique
2 LTS - Laboratory of Theoretical Spectroscopy [Tomsk]

In this work, we give improved vibration band centres predictions for ozone isotopic species including the heterogeneous isotopologues 16O3, 18O3, and the mixed 16/18 substitutions 16O16O18O, 16O18O16O, 16O18O18O, 18O16O18O in the range approaching the dissociation limit. These calculations are performed from the new ozone electronic ground state ozone potential energy surface (PES) of the ozone molecule which is built in two steps. First, ab initio electronic energies were computed following the icMRCI-AVXZ ansatz as described by Holka, Szalay, Muller and Tyuterev, J. Phys. Chem. A 2010, 114, 9927-9935, but with for much dense 3D grid and for extended range of nuclear configurations. These points were fitted with our new analytical model. At the second step lower order PES parameters were empirically optimized in the vicinity of the equilibrium configuration using experimental vibration band centres of DV ≤ 5 bands of 16O3. The predictions with this PES show better accuracy for band centres at higher energies. The improvement appears to be particularly important for the heterogeneous isotopic species. The major aim of this work is providing preliminary information for analyses of ozone isotopic vibration-rotation spectra at high wavenumber range which are currently in progress.

Domaines: Physique Atmosphérique et Océanique [physics.ao-ph]

Vladimir G. Tyuterev, Roman V. Kochanov, Sergei A. Tashkun. Analytical representation for the ozone electronic ground state potential function in the spectroscopically accessible range and extended vibration predictions. International HighRus Conference, 2012, Saint Petersburg, Russia. ⟨hal-00779256⟩