Thermodynamics of water modeled using ab initio simulations

TL;DR

This paper uses ab initio simulations to evaluate the thermodynamic properties of water, highlighting the importance of thermodynamic analysis in assessing the accuracy of electron density functionals.

Contribution

It introduces a regularized potential distribution framework to calculate water's excess free energy using BLYP-D functional, emphasizing thermodynamic assessment.

Findings

Calculated free energy aligns with experiments

Excess internal energy and entropy are less accurate

Highlights importance of thermodynamic characterization

Abstract

We regularize the potential distribution framework to calculate the excess free energy of liquid water simulated with the BLYP-D density functional. The calculated free energy is in fair agreement with experiments but the excess internal energy and hence also the excess entropy are not. Our work emphasizes the importance of thermodynamic characterization in assessing the quality of electron density functionals in describing liquid water and hydration phenomena.