q-AQUA: A Many-Body CCSD(T) Water Potential, Including Four-Body Interactions, Demonstrates the Quantum Nature of Water from Clusters to the Liquid Phase

Many model potential energy surfaces (PESs) have been reported for water; however, none are strictly from first-principles. Here we report such a potential, based on a many-body representation at the CCSD(T) level of theory up to the four-body interaction. The new PES is benchmarked for the isomers of the water hexamer for dissociation energies, harmonic frequencies, and unrestricted diffusion Monte Carlo (DMC) calculations of the zeropoint energies of the Prism, Book, and Cage isomers. Dissociation energies of several isomers of the 20-mer agree well with recent benchmark energies. Exploratory DMC calculations on this cluster verify the robustness of the new PES for quantum simulations. The accuracy and speed of the new PES are demonstrated for standard condensed phase properties, i.e., the radial distribution function and the self-diffusion constant. Quantum effects are shown to be substantial for these observables and also needed to bring theory into excellent agreement with experiment.

Automated summary

Many model potential energy surfaces for water have been reported, but none are strictly based on first-principles. This study presents a new potential energy surface for water that is based on a many-body representation at the CCSD(T) level of theory up to four-body interactions. The accuracy and speed of this new potential energy surface are demonstrated for various properties, including dissociation energies, harmonic frequencies, and quantum simulations.