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

Abstract

Using the multipolar expansion of the electrostatic energy, we characterized the asymptotic interactions between an oxygen atom O( 3P) and an oxygen molecule 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) + 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 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 O 2 thus complementing the knowledge relevant for the ozone formation mechanism. © 2012 American Institute of Physics.