Path-integral simulation of ice Ih: The effect of pressure

TL;DR

This study uses path-integral molecular dynamics to explore how pressure affects the structural and thermodynamic properties of ice Ih, revealing limits of stability and the influence of quantum effects across a range of temperatures.

Contribution

It provides a detailed analysis of pressure-induced stability limits and quantum effects on ice Ih using advanced simulation techniques.

Findings

Spinodal points at negative and positive pressures identified.

Quantum effects reduce the metastability region of ice Ih.

Pressure-dependent changes in volume, bulk modulus, and atomic delocalization observed.

Abstract

The effect of pressure on structural and thermodynamic properties of ice Ih has been studied by means of path-integral molecular dynamics simulations at temperatures between 50 and 300 K. Interatomic interactions were modeled by using the effective q-TIP4P/F potential for flexible water. Positive (compression) and negative (tension) pressures have been considered, which allowed us to approach the limits for the mechanical stability of this solid water phase. We have studied the pressure dependence of the crystal volume, bulk modulus, interatomic distances, atomic delocalization, and kinetic energy. The spinodal point at both negative and positive pressures is derived from the vanishing of the bulk modulus. For P < 0, the spinodal pressure changes from -1.38 to -0.73 GPa in the range from 50 to 300 K. At positive pressure the spinodal is associated to ice amorphization, and at low temperatures is found between 1.1 and 1.3 GPa. Quantum nuclear effects cause a reduction of the metastability region of ice Ih.