Emergence of long-range non-equilibrium correlations in free liquid diffusion

TL;DR

This paper investigates the dynamic formation of long-range concentration correlations in free liquid diffusion, revealing a new $1/r$ decay regime and confirming transient growth predictions through analytical and numerical methods.

Contribution

It introduces a model analyzing the emergence of long-range correlations in diffusion, discovering a new spatial decay regime and confirming transient growth behavior.

Findings

Identification of a $1/r$ decay regime for correlations at large distances.

Confirmation of transient growth of correlations proportional to time.

Discovery of a self-similar, quasi-steady decay regime in diffusion.

Abstract

It is experimentally well-established that non-equilibrium long-range correlations of concentration fluctuations appear in free diffusion of a solute in a solvent, but it remains unknown how such correlations are established dynamically. We address this problem in a model of Donev, Fai \& Vanden-Eijnden (DFV), obtained from the high-Schmidt limit of the Landau-Lifschitz fluctuating hydrodynamic equations for a binary mixture. We consider an initial planar interface of the mean concentration field in an infinite space domain, idealizing prior experiments. Using methods borrowed from turbulence theory, we show both analytically and numerically that a quasi-steady regime with self-similar time decay of concentration correlations appears at long time. In addition to the expected ``giant concentration fluctuations'' with correlations $\propto r$ for $r\lesssim L(t)=(Dt)^{1/2},$ with diffusivity $D,$ a new regime with spatial decay $\propto 1/r$ appears for $r\gtrsim L(t).$ The quasi-steady regime arises from an initial stage of transient growth $\propto t,$ confirming the prediction of DFV for $r\gtrsim L(t)$ and discovering an analogous result for $r\lesssim L(t).$ Our results give new insight into the emergence of non-equilibrium long-range correlations and provide novel predictions that may be investigated experimentally.