A CCSD(T)-Based 4-Body Potential for Water

High-level, ab initio calculations find that the 4-body (4-b) interaction is needed to account for near-100% of the total interaction energy for water clusters as large as the 21-mer. Motivated by this, we report a permutationally invariant polynomial potential energy surface (PES) for the 4-body interaction. This machine-learned PES is a fit to 2119 symmetry-unique, CCSD(T)-F12a/haTZ 4-b interaction energies. Configurations for these come from tetramer direct-dynamics calculations, fragments from an MD water simulation at 300 K, and tetramer fragments in a variety of water clusters. The PIP basis is purified to ensure that the PES goes rigorously to zero in monomer+trimer and dimer+dimer dissociations. The 4-b energies of isomers of the hexamer calculated with the new PES are shown to be in better agreement with benchmark CCSD(T) results than those from the MB-pol potential. Tests on larger clusters further validate the high-fidelity of the PES. The PES is shown to be fast to evaluate, taking 2.4 s for 10(5) evaluations on a single core of 2.4 GHz Intel Xeon processor, and significantly faster using a parallel version of the PES.

Automated summary

High-level ab initio calculations suggest that a 4-body interaction is crucial in describing the interaction energy of water clusters, leading to the development of a machine-learned polynomial potential energy surface (PES) for the 4-body interaction. The new PES shows improved agreement with benchmark results and faster evaluation times, demonstrating its high fidelity and efficiency in describing the interactions within water clusters.