Modeling micro-heterogeneity in mixtures: the role of many body terms

TL;DR

This paper introduces a two-component interaction model that captures micro-heterogeneity and micro-segregation in mixtures, aligning well with simulation data and offering insights into modeling complex systems like aqueous mixtures.

Contribution

The paper presents a novel two-component interaction model that separates segregation effects from random fluctuations in many-body correlations, improving theoretical and simulation agreement.

Findings

Model accurately describes micro-segregation phenomena.

Neglecting certain many-body terms enhances theory-simulation agreement.

Insights into modeling realistic systems like aqueous mixtures.

Abstract

A two-component interaction model is introduced herein, which allows to describe macroscopic miscibility with various modes of tunable micro-segregation, ranging from phase separation to micro-segregation, and in excellent agreement for structural quantities obtained from simulations and the liquid state hypernetted-chain like integral equation theory. The model is based on the conjecture that the many-body correlation bridge function term in the closure relation can be divided into one part representing the segregation effects, which are modeled herein, and the usual part representing random many body fluctuations. Furthermore, the model allows to fully neglect these second contributions, thus increasing the agreement between the simulations and the theory. The analysis of the retained part of the many body correlations gives important clues about how to model the many body bridge functions for more realistic systems exhibiting micro-segregation, such as aqueous mixtures.