PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Abstract
: The distinctive characteristics of water, evident in its thermodynamic anomalies, have implications across disciplines from biology to geophysics. Considered a valid hypothesis to rationalize its unique properties, a liquid-liquid phase transition in water below the freezing point, in the so-called supercooled regime, has nowadays been observed in several molecular dynamics simulations and is being actively researched experimentally. The hypothesis of ferroelectric phase transition in supercooled water can be traced back to 1977, due to Stillinger. In this work, we highlight intriguing and far-reaching implications of water: The ferroelectric and liquid-liquid phase transitions can be designed as two facets of the same underlying phenomenon. Our results are based on the analysis of extensive molecular dynamics simulations and are explained in the context of a classical density functional theory in mean-field approximation valid for a polar liquid, where dipolar interaction is treated perturbatively. The theory underpins the potential role of ferroelectricity in promoting the liquid-liquid phase transition, being the density-polarization coupling inherent in the dipolar interaction potential. The existence of ferroelectric order in supercooled low-density liquid water is confirmed by the observation in molecular dynamics simulations of collective modes in space-time polarization correlation functions, traceable to spontaneous breaking of continuous rotational symmetry. Our work sheds light on water's supercooled behavior and opens the door to experimental investigations of the static and dynamic behavior of water's polarization.
