Theoretical study of Cl−RG (rare gas) complexes and transport of Cl− through RG (RG = He–Rn)

We present a systematic investigation of the accuracy of the various theories and basis sets that can be applied to study the interaction of Cl− ions with Ar atoms. It is conclusively shown that gaseous ion mobility can distinguish among theoretical ion-neutral interaction potentials. Based on the conclusions, high-level ab initio potential energy curves are obtained for all of the Cl−–RG (RG = He–Rn) complexes. Spectroscopic constants have been derived from these potentials and are compared to a range of theoretical and experimental data, to which they generally show good agreement. General trends are discussed in comparison to other halogen-rare gas complexes previously studied. The potentials also have been tested by using them to calculate transport coefficients for Cl− moving through a bath of RG atoms.