Ab initio study of the O₃-N₂ complex: Potential energy surface and rovibrational states

The formation and destruction of O₃ within the Chapman cycle occurs as a result of inelastic collisions with a third body. Since N₂ is the most abundant atmospheric molecule, it can be considered as the most typical candidate when modeling energy-transfer dynamics. We report a new ab initio potential energy surface (PES) of the O₃-N₂ van der Waals complex. The interaction energies were calculated using the explicitly correlated single- and double-excitation coupled cluster method with a perturbative treatment of triple excitations [CCSD(T)-F12a] with the augmented correlation-consistent triple-zeta aug-cc-pVTZ basis set. The five-dimensional PES was analytically represented by an expansion in spherical harmonics up to eighth order inclusive. Along with the global minimum of the complex (D_e = 348.88 cm^-1), with N₂ being perpendicular to the O₃ plane, six stable configurations were found with a smaller binding energy. This PES was employed to calculate the bound states of the O₃-N₂ complex with both ortho- and para-N₂ for total angular momentum J = 0 and 1, as well as dipole transition probabilities. The nature of the bound states of the O₃-oN₂ and O₃-pN₂ species is discussed based on their rovibrational wave functions.