First-principles many-body non-additive polarization energies from monomer and dimer calculations only : A case study on water

Abstract: The many-body polarization energy is the major source of non-additivity in strongly polar systems such as water. This non-additivity is often considerable and must be included, if only in an average manner, to correctly describe the physical properties of the system. Models for the polarization energy are usually parameterized using experimental data, or theoretical estimates of the many-body effects. Here we show how many-body polarization models can be developed for water complexes using data for the monomer and dimer only using ideas recently developed in the field of intermolecular perturbation theory and state-of-the-art approaches for calculating distributed molecular properties based on the iterated stockholder atoms (ISA) algorithm. We show how these models can be calculated, and validate their accuracy in describing the many-body non-additive energies of a range of water clusters. We further investigate their sensitivity to the details of the polarization damping models used. We show how our very best polarization models yield many-body energies that agree with those computed with coupled-cluster methods, but at a fraction of the computational cost.