Pressure-Temperature Phase Diagram and $λ$-Transition in Liquid Sulfur
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arXiv
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| Format: | Preprint |
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2026
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| author | Salomoni, Sonia Datchi, Frédéric Saitta, A. Marco France-Lanord, Arthur |
| author_facet | Salomoni, Sonia Datchi, Frédéric Saitta, A. Marco France-Lanord, Arthur |
| contents | Using molecular dynamics simulations driven by a machine-learned interatomic potential, we investigate at low to intermediate pressures the $λ$-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 $λ$-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 $λ$-transition throughout the sulfur phase diagram. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2604_22696 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Pressure-Temperature Phase Diagram and $λ$-Transition in Liquid Sulfur Salomoni, Sonia Datchi, Frédéric Saitta, A. Marco France-Lanord, Arthur Chemical Physics Materials Science Soft Condensed Matter Using molecular dynamics simulations driven by a machine-learned interatomic potential, we investigate at low to intermediate pressures the $λ$-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 $λ$-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 $λ$-transition throughout the sulfur phase diagram. |
| title | Pressure-Temperature Phase Diagram and $λ$-Transition in Liquid Sulfur |
| topic | Chemical Physics Materials Science Soft Condensed Matter |
| url | https://arxiv.org/abs/2604.22696 |