A kinetic Ising model study of dynamical correlations in confined fluids: Emergence of both fast and slow time scales

TL;DR

This study uses a finite length 1D Ising model to explore how dynamical correlations propagate and decay in confined fluids, revealing the emergence of both fast and slow relaxation times consistent with experimental observations.

Contribution

Introduces a novel finite length 1D Ising model to analytically and numerically investigate dynamical correlations in confined fluids, explaining the emergence of multiple relaxation time scales.

Findings

Model reproduces experimental features of relaxation times.

Destructive interference leads to faster decay of some relaxation components.

Strong coupling results in predominantly exponential, homogeneous relaxation.

Abstract

Experiments and computer simulation studies have revealed existence of rich dynamics in the orientational relaxation of molecules in confined systems such as water in reverse micelles, cyclodextrin cavities and nano-tubes. Here we introduce a novel finite length one dimensional Ising model to investigate the propagation and the annihilation of dynamical correlations in finite systems and to understand the intriguing shortening of the orientational relaxation time that has been reported for small sized reverse micelles. In our finite sized model, the two spins at the two end cells are oriented in the opposite directions, to mimic the effects of surface that in real system fixes water orientation in the opposite directions. This produces opposite polarizations to propagate inside from the surface and to produce bulk-like condition at the centre. This model can be solved analytically for short chains. For long chains we solve the model numerically with Glauber spin flip dynamics (and also with Metropolis single-spin flip Monte Carlo algorithm). We show that model nicely reproduces many of the features observed in experiments. Due to the destructive interference among correlations that propagate from the surface to the core, one of the rotational relaxation time components decays faster than the bulk. In general, the relaxation of spins is non-exponential due to the interplay between various interactions. In the limit of strong coupling between the spins or in the limit of low temperature, the nature of relaxation of the spins undergoes a qualitative change with the emergence of a homogeneous dynamics where decay is predominantly exponential, again in agreement with experiments.