Long-range interactions in the ozone molecule: Spectroscopic and dynamical points of view

Using the multipolar expansion of the electrostatic energy, we characterized the asymptotic interactions between an oxygen atom O(3P) and an oxygen molecule [12pt]{minimal}{document}O₂(³g⁻Σ){document}O2(Σg−3), both in their electronic ground state. We calculated the interaction energy induced by the permanent electric quadrupoles of O and O2 and the van der Waals energy. On one hand, we determined the 27 electronic potential energy surfaces including spin-orbit connected to the O(3P) + [12pt]{minimal}{document}O₂(³g⁻Σ){document}O2(Σg−3) dissociation limit of the O–O2 complex. On the other hand, we computed the potential energy curves characterizing the interaction between O(3P) and a rotating [12pt]{minimal}{document}O₂(³g⁻Σ){document}O2(Σg−3) molecule in its lowest vibrational level. Such curves are found adiabatic to a good approximation, namely, they are only weakly coupled to each other. These results represent a first step for modeling the spectroscopy of ozone bound levels close to the dissociation limit, as well as the low energy collisions between O and O2 thus complementing the knowledge relevant for the ozone formation mechanism.