Pressure-Temperature Phase Diagram and $\lambda$-Transition in Liquid Sulfur

Abstract

Using molecular dynamics simulations driven by a machine-learned interatomic potential, we investigate at low to intermediate pressures the $\lambda$-transition of sulfur, a temperature-induced polymerization. At ambient pressure, we capture the melting of crystalline cyclo-octasulfur into a liquid of molecular rings. Within this liquid, the concentration of non-S$_8$ rings increases with temperature; we show that these molecules act as reactive centers, which eventually trigger polymerization. We reproduce key experimental signatures of the $\lambda$-transition, including the sharp increase in heat capacity and the pronounced dependence of the transition temperature on the heating rate. Building on this, we reconstruct a phase diagram of polymerization up to intermediate pressures. Our results reveal a moderate decrease of the polymerization temperature with pressure, culminating with its merging with the melting line at a critical point. Beyond this point, we provide direct evidence of polymerization emerging from the crystalline phase. By analyzing temperature-ramp trajectories, we observe the formation of non-S$_8$ rings, open chains, and extended polymeric structures which retain features of the crystalline arrangement; further heating the system leads to disorder taking over through melting. Polymerization is therefore initiated slightly before melting. Altogether, our findings provide a microscopic picture of the $\lambda$-transition throughout the sulfur phase diagram.