Line-shape theory of the XΣ→aΔ,bΣ transitions in O-O collision-induced absorption.

We derive the theory of collision-induced absorption for electronic transitions in the approximation of an isotropic interaction potential. We apply this theory to the spin-forbidden XΣ→aΔ and XΣ→bΣ transitions in O-O, which are relevant for calibration in atmospheric studies. We consider two mechanisms for breaking the spin symmetry, either by the intermolecular exchange interaction between paramagnetic collision partners or by the intramolecular spin-orbit coupling. The calculations for the exchange-based mechanism employ the diabatic potential energy surfaces and transition dipole moment surfaces reported in Paper I [T. Karman et al., J. Chem. Phys. 147, 084306 (2017)]. We show that the line shape of the theoretical absorption spectra is insensitive to the large uncertainty in the electronic transition dipole moment surfaces. We also perform calculations using a simple model of the alternative mechanism involving intramolecular spin-orbit coupling, which leads to absorption intensities which are well below the experimental results. The relative intensity of this spin-orbit-based mechanism may impact the relative contribution to the absorption by collisions with diamagnetic collision partners, such as the atmospherically relevant N molecule. We furthermore show that both the line shape and temperature dependence are signatures of the underlying transition mechanism.