Singularity-free interpretation of the thermodynamics of supercooled water

Abstract

The pronounced increases in isothermal compressibility, isobaric heat capacity, and in the magnitude of the thermal expansion coefficient of liquid water upon supercooling have been interpreted either in terms of a continuous, retracing spinodal curve bounding the superheated, stretched, and supercooled states of liquid water, or in terms of a metastable, low-temperature critical point. Common to these two scenarios is the existence of singularities associated with diverging density fluctuations at low temperature. We show that the increase in compressibility upon lowering the temperature of a liquid that expands on cooling, like water, is not contingent on any singular behavior, but rather is a thermodynamic necessity. We perform a thermodynamic analysis for an anomalous liquid (i.e., one that expands when cooled) in the absence of a retracing spinodal and show that one may in general expect a locus of compressibility extrema in the anomalous regime. Our analysis suggests that the simplest interpretation of the behavior of supercooled water consistent with experimental observations is free of singularities. We then develop a waterlike lattice model that exhibits no singular behavior, while capturing qualitative aspects of the thermodynamics of water.