Investigation Concerning the Uniqueness of Separatrix Lines Separating Liquidlike from Gaslike Regimes Deep in the Supercritical Phase of Water with a Focus on Widom Line Concepts

The supercritical phase of fluids has long been known to feature significantly different liquidlike and gaslike regimes. However, it is textbook knowledge that the supercritical state is a homogeneous fluid phase where properties change continuously. Nevertheless, there has been an increasing amount of evidence published that suggests that there might exist a unique line that rigorously separates different regimes in supercritical phases, particularly in the case of water. Here, we use the quasiexact IAPWS95 equation of state to rigorously assess the macroscopic thermodynamic properties of supercritical water without invoking any water model or related approximations. We focus on how these properties change deep in the supercritical phase, in particular if they allow one to introduce a unique "thermodynamic separatrix." Our rigorous thermodynamic analysis, which relies exclusively on accurate experimental data, makes clear that there is no unique separatrix in real supercritical water-such as the recently much-invoked "Widom line." A comparison to the van der Waals equation of state reproduces qualitatively all our findings for real water, thereby suggesting that our analysis should be transferable to other fluids and critical points. Topological analysis of the H-bond network structure of supercritical water, as obtained from molecular-dynamics simulations using a standard water model, demonstrates that also the percolation line does not provide a meaningful separatrix to rigorously distinguish liquidlike from gaslike regimes.