Investigation of the ArN+2 ion by dissociative ionization of argon/nitrogen clusters

The ArN+2 ion has been investigated by means of photoionization of an argon/nitrogen cluster beam in a threshold photoelectron photoion coincidence experiment. Two pathways for the formation of ArN+2 ions have been observed: (i) the nondissociative ionization of ArN2 neutrals and (ii) the dissociative ionization of Ar2N2. The two pathways are distinguished by the kinetic energy released (KER) in the dissociative ionization. The KER for the reaction Ar2N+2→ArN+2+Ar has been measured as a function of the excitation energy. The comparison of the measured KER with the statistically expected KER allows us to extrapolate to the thermochemical threshold of the reaction under investigation. A consistent picture is obtained under two assumptions: (i) the ArN+2 ion is linear and (ii) the ionization potential of ArN2 is 14.486±0.05 eV. The former assumption is confirmed by high level ab initio calculations (QCISD/6-311G*).