In this paper, we apply a theoretical model for fluid state thermodynamics to investigate simulated water in supercooled conditions. This model, which we recently proposed and applied to sub-and super-critical fluid water [Zanetti-Polzi et al., J. Chem. Phys. 156(4), 44506 (2022)], is based on a combination of the moment-generating functions of the enthalpy and volume fluctuations as provided by two gamma distributions and provides the free energy of the system as well as other relevant thermodynamic quantities. The application we make here provides a thermodynamic description of supercooled water fully consistent with that expected by crossing the liquid-liquid Widom line, indicating the presence of two distinct liquid states. In particular, the present model accurately reproduces the Widom line temperatures estimated with other two-state models and well describes the heat capacity anomalies. Differently from previous models, according to our description, a cluster of molecules that extends beyond the first hydration shell is necessary to discriminate between the statistical fluctuation regimes typical of the two liquid states.

Daidone, I., Foffi, R., Amadei, A., Zanetti-Polzi, L. (2023). A statistical mechanical model of supercooled water based on minimal clusters of correlated molecules. JOURNAL OF CHEMICAL PHYSICS ONLINE, 159(9) [10.1063/5.0157505].

A statistical mechanical model of supercooled water based on minimal clusters of correlated molecules

Andrea Amadei
;
2023-01-01

Abstract

In this paper, we apply a theoretical model for fluid state thermodynamics to investigate simulated water in supercooled conditions. This model, which we recently proposed and applied to sub-and super-critical fluid water [Zanetti-Polzi et al., J. Chem. Phys. 156(4), 44506 (2022)], is based on a combination of the moment-generating functions of the enthalpy and volume fluctuations as provided by two gamma distributions and provides the free energy of the system as well as other relevant thermodynamic quantities. The application we make here provides a thermodynamic description of supercooled water fully consistent with that expected by crossing the liquid-liquid Widom line, indicating the presence of two distinct liquid states. In particular, the present model accurately reproduces the Widom line temperatures estimated with other two-state models and well describes the heat capacity anomalies. Differently from previous models, according to our description, a cluster of molecules that extends beyond the first hydration shell is necessary to discriminate between the statistical fluctuation regimes typical of the two liquid states.
2023
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/02
English
Con Impact Factor ISI
Daidone, I., Foffi, R., Amadei, A., Zanetti-Polzi, L. (2023). A statistical mechanical model of supercooled water based on minimal clusters of correlated molecules. JOURNAL OF CHEMICAL PHYSICS ONLINE, 159(9) [10.1063/5.0157505].
Daidone, I; Foffi, R; Amadei, A; Zanetti-Polzi, L
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/346129
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