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Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/45604

Finite-size scaling investigation of the liquid-liquid critical point in ST2 water and its stability with respect to crystallization.

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The liquid-liquid critical point scenario of water hypothesizes the existence of two metastable liq- uid phases low-density liquid (LDL) and high-density liquid (HDL) deep within the supercooled region. The hypothesis originates from computer simulations of the ST2 water model, but the stabil- ity of the LDL phase with respect to the crystal is still being debated. We simulate supercooled ST2 water at constant pressure, constant temperature, and constant number of molecules N for N ≤ 729 and times up to 1 μs. We observe clear differences between the two liquids, both structural and dynamical. Using several methods, including finite-size scaling, we confirm the presence of a liquid-liquid phase transition ending in a critical point. We find that the LDL is stable with respect to the crystal in 98% of our runs (we perform 372 runs for LDL or LDL-like states), and in 100% of our runs for the two largest system sizes (N = 512 and 729, for which we perform 136 runs for LDL or LDL-like states). In all these runs, tiny crystallites grow and then melt within 1 μs. Only for N ≤ 343 we observe six events (over 236 runs for LDL or LDL-like states) of spontaneous crystal- lization after crystallites reach an estimated critical size of about 70 ± 10 molecules.

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KESSELRING, T. A., et al. Finite-size scaling investigation of the liquid-liquid critical point in ST2 water and its stability with respect to crystallization. Journal of Chemical Physics. 2013. Vol. 138, num. 24, pags. 244506-1-244506-13. ISSN 0021-9606. [consulted: 8 of August of 2026]. Available at: https://hdl.handle.net/2445/45604

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