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Spectroscopic constants, obtained using two-color optical double resonance via repulsive intermediate states, are presented for four ion-pair states of Cl 2 ; i.e., the E(0 g ϩ ), ␤͑1 g ͒, f (0 g ϩ ), and G(1 g ) states. One-color excitation, also via a repulsive intermediate state, has been used to further extend the vibrational data for the ␤͑1 g ͒ state. The same pumping scheme has been used to extend a vibrational progression in the ͓ 2 ⌸ 1/2 ͔ c 4s; 1 g Rydberg state. The absence of perturbations when the ͓ 2 ⌸ 1/2 ͔ c 4s; 1 g Rydberg and the ␤͑1 g ͒ ion-pair states cross, together with the key role played by the intermediate C(1 u ) state in accessing both singlet and triplet final states, are discussed in terms of the changes in spin-orbital coupling schemes that are required on bond stretching.

Mass-resolved multiphoton ionization spectroscopy of jet-cooled Cl-2-.2. The (2+1) REMPI spectrum between 76000 and 90000 cm(-1)