Phase diagram of heteronuclear Janus dumbbells

TL;DR

This study maps the phase diagram of heteronuclear Janus dumbbells with variable sphere sizes and interactions, revealing how phase behavior transitions from fluid-like to self-assembled structures as size asymmetry increases.

Contribution

It provides the first detailed phase diagram classification of heteronuclear Janus dumbbells across different size ratios and interaction regimes.

Findings

Gas-liquid phase separation dominates at high size ratios near 2.

Self-assembled structures emerge as size asymmetry increases.

Gas-liquid transition becomes metastable below a certain size ratio.

Abstract

Using Aggregation-Volume-Bias Monte Carlo simulations along with Successive Umbrella Sampling and Histogram Re-weighting, we study the phase diagram of a system of dumbbells formed by two touching spheres having variable sizes, as well as different interaction properties. The first sphere ($h$) interacts with all other spheres belonging to different dumbbells with a hard-sphere potential. The second sphere ($s$) interacts via a square-well interaction with other $s$ spheres belonging to different dumbbells and with a hard-sphere potential with all remaining $h$ spheres. We focus on the region where the $s$ sphere is larger than the $h$ sphere, as measured by a parameter $1\le \alpha\le 2 $ controlling the relative size of the two spheres. As $\alpha \to 2$ a simple fluid of square-well spheres is recovered, whereas $\alpha \to 1$ corresponds to the Janus dumbbell limit, where the $h$ and $s$ spheres have equal sizes. Many phase diagrams falling into three classes are observed, depending on the value of $\alpha$. The $1.8 \le \alpha \le 2$ is dominated by a gas-liquid phase separation very similar to that of a pure square-well fluid with varied critical temperature and density. When $1.3 \le \alpha \le 1.8$ we find a progressive destabilization of the gas-liquid phase diagram by the onset of self-assembled structures, that eventually lead to a metastability of the gas-liquid transition below $\alpha=1.2$.