The isotopomer-resolved vibrational and spin-orbit energy structures of Cl2+(X̃Πg2) have been studied by one-photon zero kinetic energy photoelectron spectroscopy. The spin-orbit energy splitting for the ground vibrational state is determined as 717.7±1.5cm1, which greatly improves on the accuracy of the previously reported data. This value is found to be in good agreement with the ab initio quantum chemical calculation taking account of the inner shell electron correlation. The first adiabatic ionization energy (IE) of Cl2 is determined as 92645.9±1.0cm1. Using the ion-pair formation imaging method to discriminate signals of Cl+(D21) from those of Cl+(Pj3), the threshold for ion-pair (Etipp) production, Cl+(D21)+Cl(S01)Cl2(XΣg+1), is determined as 1070962+8cm1. By using the determined IE and Etipp for Cl2 and also the reported IE and electronic affinity for chlorine atom, the bond dissociation energies of Cl2(XΣg+1) and Cl2+(X̃Πg2) have been determined as 199902+8 and 31935.12+8, respectively.

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