A systematic ab initio study of the water dimer in hierarchies of basis sets and correlation models

Abstract.

A systematic, high-level ab initio investigation of the water dimer has been performed. The oxygen-oxygen bond distance has been estimated to be around 2.90 Å, about 0.05 Å shorter than the experimentally estimated distance, challenging the accuracy of the latter. The interaction energy has been obtained at −5.0±0.1 kcal/mol, which compares favourably with the experimentally estimated value of −5.4±0.7 kcal/mol. The importance of employing basis sets that include diffuse functions in correlated calculations on hydrogen-bonded systems is confirmed. In correlated calculations on the water dimer and the hydrogen fluoride dimer, the counterpoise-corrected interaction energies converge considerably slower towards the basis set limit than do the uncorrected energies, provided that the correlation-consistent basis sets are augmented with diffuse functions.