We perform an accurate analysis of the density self-correlation functions of TIP4P/2005 supercooled water on approaching the region of the liquid-liquid critical point. In a previous work on this model, we provided evidence of a fragile to strong crossover of the dynamical behavior in the deep supercooled region. The structural relaxation follows the Mode Coupling theory in the fragile region and then deviates from Mode Coupling regime to a strong Arrhenius behavior. This crossover is particularly important in water because it is connected to the thermodynamics of the supercooled region. To better understand the origin of this crossover, we compute now the Van Hove self-correlation functions. In particular we aim at investigating the presence and the role of the hopping phenomena that are the cause of the fragile to strong crossover in simple liquids. In TIP4P/2005 water, we find hopping processes too and we analyze how they depend on temperature and density upon approaching the fragile to strong crossover and the Mode Coupling ideal crossover temperature. Our results show that water behaves like a simple glass former. After an initial ballistic regime, the cage effect dominates the mild supercooled region, with diffusion taking place at long time. At the fragile to strong crossover, we find that hopping (activated) processes start to play a role. This is evidenced by the appearance of peaks in the Van Hove correlation functions. In the deep supercooled regime, our analysis clearly indicates that activated processes dominate the dynamics. The comparison between the Van Hove functions and the radial distribution functions allows to better understand the mechanism of hopping phenomena in supercooled water and to connect their onset directly with the crossing of the Widom Line.

DE MARZIO, M., Camisasca, G., Rovere, M., Gallo, P. (2017). Microscopic origin of the fragile to strong crossover in supercooled water: The role of activated processes. THE JOURNAL OF CHEMICAL PHYSICS, 146(8), 084502 [10.1063/1.4975387].

Microscopic origin of the fragile to strong crossover in supercooled water: The role of activated processes

DE MARZIO, MARGHERITA;CAMISASCA, GAIA;ROVERE, Mauro;GALLO, PAOLA
2017-01-01

Abstract

We perform an accurate analysis of the density self-correlation functions of TIP4P/2005 supercooled water on approaching the region of the liquid-liquid critical point. In a previous work on this model, we provided evidence of a fragile to strong crossover of the dynamical behavior in the deep supercooled region. The structural relaxation follows the Mode Coupling theory in the fragile region and then deviates from Mode Coupling regime to a strong Arrhenius behavior. This crossover is particularly important in water because it is connected to the thermodynamics of the supercooled region. To better understand the origin of this crossover, we compute now the Van Hove self-correlation functions. In particular we aim at investigating the presence and the role of the hopping phenomena that are the cause of the fragile to strong crossover in simple liquids. In TIP4P/2005 water, we find hopping processes too and we analyze how they depend on temperature and density upon approaching the fragile to strong crossover and the Mode Coupling ideal crossover temperature. Our results show that water behaves like a simple glass former. After an initial ballistic regime, the cage effect dominates the mild supercooled region, with diffusion taking place at long time. At the fragile to strong crossover, we find that hopping (activated) processes start to play a role. This is evidenced by the appearance of peaks in the Van Hove correlation functions. In the deep supercooled regime, our analysis clearly indicates that activated processes dominate the dynamics. The comparison between the Van Hove functions and the radial distribution functions allows to better understand the mechanism of hopping phenomena in supercooled water and to connect their onset directly with the crossing of the Widom Line.
DE MARZIO, M., Camisasca, G., Rovere, M., Gallo, P. (2017). Microscopic origin of the fragile to strong crossover in supercooled water: The role of activated processes. THE JOURNAL OF CHEMICAL PHYSICS, 146(8), 084502 [10.1063/1.4975387].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11590/318190
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