Optical population of gerade and ungerade iodine ion-pair states via MI2 vdW complexes of valence states correlating with the third dissociation limit, MÂ =Â I2, Xe

► We populated gerade and underade ion-pair states in three-step, two-color transitions. ► We measured excitation spectra of luminescence from these states. ► We discussed possible mechanisms of population of the states. ► We conclude that the mechanism including vdW complexes is the most probable.