Contribution of many-body terms to the energy for small water clusters: A comparison of ab initio calculations and accurate model potentials

We have tested the ability of two new model potentials constructed using intermolecular perturbation theory methods to reproduce ab initio results at a comparable level of theory. Several configurations of water trimer, tetramer, and pentamer are studied, and in addition to the contributions to the interaction energy, the potential energy surfaces are compared by optimizing the model potential geometries to local stationary points within a rigid-body framework. In general the agreement between the two methods is good, validating the model potentials as suitable candidates for providing starting geometries for further ab initio calculations and for the simulation of larger systems.