An Equation of State For The TIP4P/2005 Model of Water Including Negative Pressures

TL;DR

This paper develops an equation of state for the TIP4P/2005 water model that accurately describes its behavior at both positive and negative pressures, incorporating a liquid-vapor spinodal and two-structure thermodynamics.

Contribution

It introduces a two-structure equation of state including a liquid-vapor spinodal that matches simulation data across a broad pressure range, explaining water anomalies without a retracing spinodal.

Findings

The equation reproduces density, compressibility, and heat capacity minima and maxima.

The liquid-vapor spinodal in the model is monotonic, not retracing.

Water anomalies are explained by two-structure competition and a monotonic spinodal.

Abstract

One of the most promising frameworks for understanding the anomalies of cold and especially supercooled water is that of two-structure thermodynamics, in which water is viewed as a non-ideal mixture of two interconvertible local structures. The non-ideality of this mixture may give rise, at very low temperatures, to a liquid-liquid phase transition (LLPT) and a liquid-liquid critical point (LLCP), at which thermodynamic response functions diverge. Various versions of the "two-structure equation of state" (TSEOS) based on this concept have shown remarkable agreement with both experimental data in real water and simulation results. However, recent experiments probing supercooled water at negative pressures reveal the inadequacy of extrapolations of equations of state developed for positive pressures, and have begun to shed additional light on the source of the anomalies of supercooled water. We have analyzed simulation results for the TIP4P/2005 model over a broad range of positive and negative pressures from ambient temperature to deep supercooling. We find that by explicitly incorporating a liquid-vapor spinodal into a two-structure equation of state, we are able to match the simulation data in TIP4P/2005 with striking accuracy. In particular, our equation of state reproduces the observed lines of minima and maxima in the density, isothermal compressibility, and isobaric heat capacity. Contrary to scenarios in which a retracing spinodal accounts for the thermodynamic anomalies of water, we find that the liquid-vapor spinodal in this model continues monotonically to lower pressures as temperature is decreased, influencing but not giving rise to the locus of density maxima and other thermodynamic anomalies. We explain the behavior of TIP4P/2005 in terms of two phenomena: the competition between two local structures and a monotonic liquid-vapor spinodal.