Benchmark free energies and entropies for saturated and compressed water

TL;DR

This study uses advanced molecular simulation techniques to accurately compute free energies and entropies for various water models across different thermodynamic states, providing insights into their performance and agreement with experimental data.

Contribution

It introduces a benchmark-free energy and entropy calculation method for multiple water models using Expanded Wang-Landau simulations, offering detailed thermodynamic property comparisons.

Findings

SPC/E, TIP4P/2005, TIP4P/Ew best for vapor-liquid equilibrium

TIP4P/Ew model most accurately captures compressed water properties

Simulation results align well with experimental data for entropy and Gibbs free energy

Abstract

We use molecular simulation to compute the thermodynamic properties of 7 rigid models for water (SPC/E, TIP3P, TIP4P, TIP4P/2005, TIP4P/Ew, TIP5P, OPC) over a wide range of temperature and pressure. Carrying out Expanded Wang-Landau simulations, we obtain a high accuracy estimate for the grand-canonical partition function which, in turn, provides access to all properties, including the free energy and entropy, both at the vapor-liquid coexistence and for compressed water. The results at coexistence highlight the close connection between the behavior of the statistical functions and the thermodynamic properties. They show that the subgroup (SPC/E,TIP4P/2005,TIP4P/Ew) provides the most accurate account of the vapor-liquid equilibrium properties. For compressed water, the comparison of the simulation results to the experimental data establishes that the TIP4P/Ew model performs best among the 7 models considered here, and captures the experimental trends for the dependence of entropy and molar Gibbs free energy on pressure.