Phase diagram of heteronuclear Janus dumbbells

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 $\alpha =1.2$.

16 pages, 14 Figures, accepted for publication in Soft Matter