On the Different Faces of the Supercritical Phase of Water at a Near-Critical Temperature: Pressure-Induced...

The present study reports a systematic analysis of a wide variety of structural, thermodynamic, and dynamic properties of supercritical water along the near-critical isotherm of T = 1.03T_c and up to extreme pressures, using molecular dynamics and Monte Carlo simulations. The methodology employed provides solid evidence about the existence of a structural transition from a liquidlike fluid to a compressed, tightly packed liquid, in the density and pressure region around 3.4ρ_c and 1.17 GPa, introducing an alternative approach to locate the crossing of the Frenkel line. Around 8.5 GPa another transition to a face-centered-cubic plastic crystal polymorph with density 5.178ρ_c is also observed, further confirmed by Gibbs free energy calculations using the two-phase thermodynamic model. The isobaric heat capacity maximum, closely related to the crossing of the Widom line, has also been observed around 0.8ρ_c, where the local density augmentation is also maximized. Another structural transition has been observed at 0.2ρ_c, related to the transformation of the fluid to a dilute gas at lower densities. These findings indicate that a near-critical isotherm can be divided into different domains where supercritical water exhibits distinct behavior, ranging from a gaslike one to a plastic crystal one.