Interaction energies for the water dimer by supermolecular methods and symmetry-adapted perturbation theory: the role of bond functions and convergence of basis subsets

Abstract

Using a systematic series of basis sets in supermolecular and symmetry-adapted intermolecular perturbation theory calculations it is examined how interaction energies of various water dimer structures change upon addition and shifting of bond functions. Their addition to augmented double- and triple-zeta basis sets brings the sum of the electron correlation contributions to the second-order interaction energy nearly to convergence, while accurate first-order electrostatic and exchange contributions require better than augmented quadruple-zeta quality. A scheme which combines the different perturbation energy contributions as computed in different basis subsets performs uniformly well for the various dimer structures. It yields a symmetry-adapted perturbation theory value of −21.08 kJ/mol for the energy of interaction of two vibrationally averaged water molecules compared to −21.29 kJ/mol when the full augmented triple-zeta basis set is used throughout.