Predictions for water clusters from a first-principles two- and three-body force field

Abstract

A new rigid-monomer three-body potential has been developed for water by fitting it to more than 70 thousand trimer interaction energies computed ab initio using coupled-cluster methods and augmented triple-zeta-quality basis sets. This potential was used together with a modified form of a previously developed two-body potential and with a polarization model of four- and higher-body interactions to predict the energetics of the water trimer, hexamer, and 24-mer. Despite using the rigid-monomer approximation, these predictions agree better with flexible-monomer benchmarks than published results obtained with flexible-monomer force fields. An unexpected finding of our work is that simple polarization models predict four-body interactions to within a few percent, whereas for three-body interactions these models are known to have errors on the order of 50%. © 2014 AIP Publishing LLC.