Role of hydrodynamics in liquid–liquid transition of a single-component substance

Abstract

Liquid–liquid transition (LLT) is an unconventional transition between two liquid states in a single-component system. This phenomenon has recently attracted considerable attention not only because of its counterintuitive nature but also since it is crucial for our fundamental understanding of the liquid state. However, its physical understanding has remained elusive, particularly of the critical dynamics and phase-ordering kinetics. So far, the hydrodynamic degree of freedom, which is the most intrinsic kinetic feature of liquids, has been neglected in its theoretical description. Here we develop a Ginzburg–Landau-type kinetic theory of LLT taking it into account, based on a two-order parameter model. We examine slow critical fluctuations of the nonconserved order parameter coupled to the hydrodynamic degree of freedom in equilibrium. We also study the nonequilibrium process of LLT. We show both analytically and numerically that domain growth becomes faster (slower), depending upon the density decrease (increase) upon the transition, as a consequence of hydrodynamic flow induced by the density change. The coupling between nonconserved order parameter and hydrodynamic interaction results in anomalous domain growth in both nucleation-growth–type and spinodal-decomposition–type LLT. Our study highlights the characteristic features of hydrodynamic fluctuations and phase ordering during LLT under complex interplay among conserved and nonconserved order parameters and the hydrodynamic transport intrinsic to the liquid state.