On the accuracy of the MB-pol many-body potential for water: Interaction energies, vibrational frequencies, and classical thermodynamic and dynamical properties from clusters to liquid water and ice

TL;DR

This study systematically evaluates the MB-pol many-body potential's accuracy in modeling water across gas, liquid, and ice phases, showing excellent agreement with experimental and high-level theoretical data for energies, spectra, and thermodynamic properties.

Contribution

The paper provides a comprehensive validation of MB-pol's accuracy for water's interaction energies, vibrational spectra, and thermodynamic properties across all phases, highlighting its unprecedented precision.

Findings

MB-pol accurately reproduces water cluster interaction energies and vibrational spectra.

Structural and thermodynamic properties of liquid water match experimental data closely.

MB-pol correctly predicts densities and lattice energies of various ice phases.

Abstract

The MB-pol many-body potential has recently emerged as an accurate molecular model for water simulations from the gas to the condensed phase. In this study, the accuracy of MB-pol is systematically assessed across the three phases of water through extensive comparisons with experimental data and high-level ab initio calculations. Individual many-body contributions to the interaction energies as well as vibrational spectra of water clusters calculated with MB-pol are in excellent agreement with reference data obtained at the coupled cluster level. Several structural, thermodynamic, and dynamical properties of the liquid phase at atmospheric pressure are investigated through classical molecular dynamics simulations as a function of temperature. The structural properties of the liquid phase are in nearly quantitative agreement with X-ray diffraction data available over the temperature range from 268 to 368 K. The analysis of other thermodynamic and dynamical quantities emphasizes the importance of explicitly including nuclear quantum effects in the simulations, especially at low temperature, for a physically correct description of the properties of liquid water. Furthermore, both densities and lattice energies of several ice phases are also correctly reproduced by MB-pol. Following a recent study of DFT models for water, a score is assigned to each computed property, which demonstrates the high and, in many respects, unprecedented accuracy of MB-pol in representing all three phases of water.