Path-integral simulation of ice VII: Pressure and temperature effects

TL;DR

This study uses path-integral molecular dynamics to explore how pressure and temperature influence the structural and thermodynamic properties of ice VII, revealing the limits of quasi-harmonic approximation accuracy under varying conditions.

Contribution

It provides a detailed analysis of ice VII's properties under different pressures and temperatures using PIMD, comparing results with QHA to evaluate anharmonic effects.

Findings

QHA accuracy decreases with rising temperature

QHA becomes more reliable at higher pressures

Anharmonic effects are less significant at high pressures

Abstract

Effects of pressure and temperature on structural and thermodynamic properties of ice VII have been studied by using path-integral molecular dynamics (PIMD) simulations. Temperatures between 25 and 450 K, as well as pressures up to 12 GPa were considered. Interatomic interactions were modeled by using the effective q-TIP4P/F potential for flexible water. We analyze the pressure dependence of the molar volume, bulk modulus, interatomic distances, kinetic energy, and atomic delocalization at various temperatures. Results of PIMD simulations are compared with those derived from a quasi-harmonic approximation (QHA) of vibrational modes, which helps to assess the importance of anharmonic effects, as well as the influence of the different modes on the properties of ice VII. The accuracy of the QHA for describing this high-pressure phase decreases for rising temperature, but this approximation becomes more reliable as pressure grows, since anharmonicity becomes less relevant. Comparisons with low-pressure cubic ice are presented.