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

Abstract

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) spinodalmore » 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.« less

Authors:
 [1];  [2];  [1];  [3];  [4];  [1]
  1. Departamento Química Física I, Facultad Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain)
  2. (United Kingdom)
  3. (Spain)
  4. Institut Lumière Matière, UMR5306 Université Claude Bernard Lyon 1-CNRS, Université de Lyon, 69622 Villeurbanne Cedex (France)
Publication Date:
OSTI Identifier:
22679030
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 145; Journal Issue: 5; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPUTERIZED SIMULATION; EXPERIMENTAL DATA; PHASE DIAGRAMS; RESPONSE FUNCTIONS; SPECIFIC HEAT; THERMODYNAMICS

Citation Formats

González, Miguel A., Department of Chemistry, Imperial College London, London SW7 2AZ, Valeriani, Chantal, Departamento Física Aplicada I, Facultad Ciencias Físicas, Universidad Complutense de Madrid, 28040 Madrid, Caupin, Frédéric, and Abascal, José L. F. A comprehensive scenario of the thermodynamic anomalies of water using the TIP4P/2005 model. United States: N. p., 2016. Web. doi:10.1063/1.4960185.
González, Miguel A., Department of Chemistry, Imperial College London, London SW7 2AZ, Valeriani, Chantal, Departamento Física Aplicada I, Facultad Ciencias Físicas, Universidad Complutense de Madrid, 28040 Madrid, Caupin, Frédéric, & Abascal, José L. F. A comprehensive scenario of the thermodynamic anomalies of water using the TIP4P/2005 model. United States. doi:10.1063/1.4960185.
González, Miguel A., Department of Chemistry, Imperial College London, London SW7 2AZ, Valeriani, Chantal, Departamento Física Aplicada I, Facultad Ciencias Físicas, Universidad Complutense de Madrid, 28040 Madrid, Caupin, Frédéric, and Abascal, José L. F. Sun . "A comprehensive scenario of the thermodynamic anomalies of water using the TIP4P/2005 model". United States. doi:10.1063/1.4960185.
@article{osti_22679030,
title = {A comprehensive scenario of the thermodynamic anomalies of water using the TIP4P/2005 model},
author = {González, Miguel A. and Department of Chemistry, Imperial College London, London SW7 2AZ and Valeriani, Chantal and Departamento Física Aplicada I, Facultad Ciencias Físicas, Universidad Complutense de Madrid, 28040 Madrid and Caupin, Frédéric and Abascal, José L. F.},
abstractNote = {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.},
doi = {10.1063/1.4960185},
journal = {Journal of Chemical Physics},
number = 5,
volume = 145,
place = {United States},
year = {Sun Aug 07 00:00:00 EDT 2016},
month = {Sun Aug 07 00:00:00 EDT 2016}
}