An a b i n i t i o study of hydrated chloride ion complexes: Evidence of polarization effects and nonadditivity

An ab initio study of complexes involving a chloride ion with one through six water molecules is presented. Calculations are performed using an RHF/6-31+G(D) theoretical model and partially optimized geometries. Chloride–water interaction energies are computed with a correction for basis set superposition. Polarization of the chloride ion by increasing numbers of water molecules causes a decrease from linearity among the energies. For the six water case, deviation from two-body additivity is approximately 10% of the stabilization energy.