The lowest electronic states of Ne2 +, Ar2 + and Kr2 +: comparison of theory and experiment

Abstract

Non-relativistic configuration interaction (CI) ab initio calculations using large basis sets have been carried out to determine the potential curves of the first electronic states of Ne2 +, Ar2 + and Kr2 +. The spin—orbit interaction was treated assuming that the spin—orbit coupling constant is independent of the internuclear separation (R). For Ar2 +, calculated dissociation energies and equilibrium separations are in good agreement with experimental results. The calculations for Ne2 + suggest that the lowest vibrational level of the I(1/2u) ground state observed by threshold photoelectron spectroscopy by Hall et al. [1995, J. Phys. B: At. molec. opt. Phys., 28, 2435] and assigned to either ν = 0 or ν = 2 actually corresponds to ν = 4. The calculations also predict the I(1/2g) state of Ne2 + and Ar2 + to possess a double-well potential and that of Kr2 + to be repulsive at short range and to only possess a single shallow well at large internuclear separation. The ab initio calculations provide an explanation for the observation made by Yoshii et al. [2002, J. chem. Phys., 117, 1517] that Kr2 + and Xe2 + dissociate after photoemission from the II(1/2u) state to the I(1/2g) state whereas Ar2 + does not.