Phase behaviour and structure of a superionic liquid in nonpolarized nanoconfinement

TL;DR

This paper develops a statistical theory and performs simulations to explore the phase behavior and structure of superionic liquids confined in ultranarrow metallic pores, revealing ordered and disordered phases and their transitions.

Contribution

It introduces an analytical bipartite lattice model for superionic liquids in nanoconfinement and validates findings with Monte Carlo simulations, highlighting phase transitions and structural patterns.

Findings

Existence of ordered and disordered phases in confined superionic liquids

Phase transition can be first or second order depending on parameters

Formation of ionic clusters and snake-like patterns observed in simulations

Abstract

The ion-ion interactions become exponentially screened for ions confined in ultranarrow metallic pores. To study the phase behaviour of an assembly of such ions, called a superionic liquid, we develop a statistical theory formulated on bipartite lattices, which allows an analytical solution within the Bethe-lattice approach. Our solution predicts the existence of ordered and disordered phases in which ions form a crystal-like structure and a homogeneous mixture, respectively. The transition between these two phases can potentially be first or second order, depending on the ion diameter, degree of confinement and pore ionophobicity. We supplement our analytical results by three-dimensional off-lattice Monte Carlo simulations of an ionic liquid in slit nanopores. The simulations predict formation of ionic clusters and ordered snake-like patterns, leading to characteristic close-standing peaks in the cation-cation and anion-anion radial distribution functions.