A comprehensive scenario of the thermodynamic anomalies of water using the TIP4P/2005 model

Journal Article · Sun Aug 07 04:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4960185· OSTI ID:22679030

González, Miguel A. ^[1]; Valeriani, Chantal ^[1]; Caupin, Frédéric ^[2]; Abascal, José L. F. ^[1]

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1. Departamento Química Física I, Facultad Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain)
2. Institut Lumière Matière, UMR5306 Université Claude Bernard Lyon 1-CNRS, Université de Lyon, 69622 Villeurbanne Cedex (France)

The striking behavior of water has deserved it to be referred to as an “anomalous” liquid. The water anomalies are greatly amplified in metastable (supercooled and/or stretched) regions. This makes difficult a complete experimental description since, beyond certain limits, the metastable phase necessarily transforms into the stable one. Theoretical interpretation of the water anomalies could then be based on simulation results of well validated water models. But the analysis of the simulations has not yet reached a consensus. In particular, one of the most popular theoretical scenarios—involving the existence of a liquid-liquid critical point (LLCP)—is disputed by several authors. In this work, we propose to use a number of exact thermodynamic relations which may shed light on this issue. Interestingly, these relations may be tested in a region of the phase diagram which is outside the LLCP thus avoiding the problems associated to the coexistence region. The central property connected to other water anomalies is the locus of temperatures at which the density along isobars attain a maximum (TMD line) or a minimum (TmD). We have performed computer simulations to evaluate the TMD and TmD for a successful water model, namely, TIP4P/2005. We have also evaluated the vapor-liquid (VL) spinodal in the region of large negative pressures. The shape of these curves and their connection to the extrema of some response functions, in particular the isothermal compressibility and heat capacity at constant pressure, provides very useful information which may help to elucidate the validity of the theoretical proposals. In this way, we are able to present for the first time a comprehensive scenario of the thermodynamic water anomalies for TIP4P/2005 and their relation to the vapor-liquid spinodal. The overall picture shows a remarkable similarity with the corresponding one for the ST2 water model, for which the existence of a LLCP has been demonstrated in recent years. It also provides a hint as to where the long-sought for extrema in response functions might become accessible to experiments.

• OSTI ID: 22679030
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 145; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
COMPUTERIZED SIMULATION
EXPERIMENTAL DATA
PHASE DIAGRAMS
RESPONSE FUNCTIONS
SPECIFIC HEAT
THERMODYNAMICS