Phase behavior of metastable water based on fully ab initio simulations

Abstract

Based on the strongly constrained and appropriately normed (SCAN) functional, phase behavior of metastable water is studied by ab initio molecular dynamics simulations. A clear van der Waals loop or two-phase coexistence line is observed in the simulated isotherms from 230 to 380 K, providing ab initio evidence for a first-order phase transition. The stability limit line formed by connecting the calculated spinodal points is observed to be a continuous reentrant curve, and the liquid-liquid critical point appears to be hidden at its minimum. The line of maximum density also tends to end at this minimum. These results suggest that the phase behavior of metastable water favors a critical-point-free scenario. Due to the potential limitations of the SCAN functional itself and the failure to take nuclear quantum effects into account, it remains to be further investigated whether the phase behavior of real water remains as predicted in the present work.