Free energy calculations and unbiased dynamics reveal a continuous liquid-liquid transition in water no man's land (2106.08263v1)

Abstract: The existence of a first-order phase transition between a low-density liquid (LDL) and a high-density liquid (HDL) forms of supercooled water has been a central and highly debated issue of physics and chemistry in the last three decades. We present a computational study that allows to determine the free-energy landscapes of supercooled water over a wide range of pressure and temperature conditions, using the accurate TIP4P/2005 force field. Our approach combines topology-based structural transformation coordinates, state-of-the-art free-energy calculation methods, and extensive unbiased molecular dynamics simulations. All our results indicate that transitions between the LDL and HDL forms are smooth throughout the so-called "no man's land", and that free-energy barriers do not appear until the onset of the solid, non-diffusive amorphous forms.