Observation of a reentrant structural transition in an arsenic sulfide liquid

A fundamental and much-debated issue in glass science is the existence and nature of liquid-liquid transitions in glass-forming liquids. Here, we report the existence of a novel reentrant structural transition in a S-rich arsenic sulfide liquid of composition As_2.5S_97.5. The nature of this transition and its effect on viscosity are investigated in situ using a combination of differential scanning calorimetry and simultaneous Raman spectroscopic and rheometric measurements. The results indicate that, upon heating significantly above its glass transition temperature (261 K), the constituent S_n sulfur chains in the structure of the supercooled liquid first undergo a S_n⇌S₈ chain-to-ring conversion near ∼383 K, which is exothermic in nature. Further heating above 393 K alters the equilibrium to shift in the opposite direction toward an endothermic ring-to-chain conversion characteristic of the well-known λ-transition in pure sulfur liquid. This behavior is attributed to the competing effects of enthalpy of mixing and conformational entropy of ring and chain elements in the liquid. The existence of reentrant structural transitions in glass-forming liquids could provide important insights into the thermodynamics of liquid-liquid transitions and may have important consequences for harnessing novel functionalities of derived glasses.