Water at negative pressure: Nuclear quantum effects

TL;DR

This study investigates nuclear quantum effects on water's physical properties and stability limits under extreme conditions using path-integral molecular dynamics simulations, revealing quantum-induced shifts in the liquid-gas spinodal pressure.

Contribution

It provides the first detailed quantification of nuclear quantum effects on water's mechanical stability and properties under negative pressure conditions.

Findings

Quantum effects shift the spinodal pressure by about 10-15 MPa.

Nuclear quantum motion affects molar volume and bond angles.

Quantum simulations identify the stability limits of liquid water at various temperatures.

Abstract

Various condensed phases of water, spanning from the liquid state to multiple ice phases, have been systematically investigated under extreme conditions of pressure and temperature to delineate their stability boundaries. This study focuses on probing the mechanical stability of liquid water through path-integral molecular dynamics simulations, employing the q-TIP4P/F potential to model interatomic interactions in flexible water molecules. Temperature and pressure conditions ranging from 250 to 375 K and -0.3 to 1 GPa, respectively, are considered. This comprehensive approach enables a thorough exploration of nuclear quantum effects on various physical properties of water through direct comparisons with classical molecular dynamics results employing the same potential model. Key properties such as molar volume, intramolecular bond length, H--O--H angle, internal and kinetic energy are analyzed, with a specific focus on the effect of tensile stress. Particular attention is devoted to the liquid-gas spinodal pressure, representing the limit of mechanical stability for the liquid phase, at several temperatures. The quantum simulations reveal a spinodal pressure for water of -286 and -236 MPa at temperatures of 250 and 300 K, respectively. At these temperatures, the discernible shifts induced by nuclear quantum motion are quantified at 15 and 10 MPa, respectively. These findings contribute valuable insights into the interplay of quantum effects on the stability of liquid water under diverse thermodynamic conditions.