Development of a “First Principles” Water Potential with Flexible Monomers. II: Trimer Potential Energy Surface, Third Virial Coefficient, and Small Clusters

A full-dimensional potential energy function (MB-pol) for simulations of water from the dimer to bulk phases is developed entirely from “first principles” by building upon the many-body expansion of the interaction energy. Specifically, the MB-pol potential is constructed by combining a highly accurate dimer potential energy surface [J. Chem. Theory Comput. 2013, 9, 5395] with explicit three-body and many-body polarization terms. The three-body contribution, expressed as a combination of permutationally invariant polynomials and classical polarizability, is derived from a fit to more than 12000 three-body energies calculated at the CCSD­(T)/aug-cc-pVTZ level of theory, imposing the correct asymptotic behavior as predicted from “first principles”. Here, the accuracy of MB-pol is demonstrated through comparison of the calculated third virial coefficient with the corresponding experimental data as well as through analysis of the relative energy differences of small clusters.