Nucleation and anomalous properties of pure and salty water...is the water force field accurate...
Transcript of Nucleation and anomalous properties of pure and salty water...is the water force field accurate...
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NNucleation and anomalous properties ucleation and anomalous properties of pure and salty waterof pure and salty water
Jose L. F. Abascal
Depto. Quimica-Fisica I, Univ. Complutense Madrid
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Motivation
Liquid-liquid critical point
(retracing TMD)
Stability limit conjecture
(retracing spinodal)
In 1976 Speedy and Angell provided experimental evidence of a divergence in the isothermal compressibility of supercooled water
Possible Scenarios
The interesting region lies in the no man's land, not accessible to experiment because it is beyond the homogeneous nucleation line
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The no man's land region
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A difficult puzzle to solve
Because of the experimental difficulties (no man's land region), numerical simulation may provide important information
but …
is the water force field accurate enough?
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TIP4P/2005
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Performance of TIP4P/2005
VLE
Surface Tension Self Diffusion Coefficient
Shear Viscosity
EOS high pressure
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C. Vega and J.L.F. Abascal, PCCP 13, 19663 (2011)
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Temperature of maximum density (TIP4P/2005 vs experiment)
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The doubly metastable region
It is possible to cross the (κT) Widom line before the system nucleates!
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Speed of sound
Experiment
Simulation
This is the first experimental report of extremafor a response function in supercooled bulk water!
Pallares et al., PNAS 111, 7936 (2014)
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Isothermal compressibility
Positive pressures
Negative pressures
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Maxima and minima collapse below -100 MPa
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Scenario of water anomalies for TIP4P/2005 (I)
J.L.F. Abascal WaterSpain2013 - Zaragoza
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Scenario of water anomalies for TIP4P/2005 (I)
J.L.F. Abascal WaterSpain2013 - Zaragoza
Singularity free scenario must be ruled out
TIP4P/2005 results compatible with the liquidliquid critical point hypothesis
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Temperature of minimum density (TmD)
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Positive pressures Negative pressures
Density minima are featured in the stretched region
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TmD and heat capacity extrema (Cp)
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The maxima and minima of Cp appear only in the supercooled region
(usually, in the doubly metastable region)
Density minima are featured in the stretched region
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Full scenario of water anomalies (TIP4P/2005)
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The liquidliquid critical point scenario seems plausible but it could also be possible
that Tc = 0 K
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Relevance of ice nucleation
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nucle
ación
crecimiento
Homogeneous nucleation: free energy and nucleation rate
Z: Zeldovich factor
f+: attachment rate
ρl: liquid density
Classical nucleation theory (CNT):
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Generation of a spherical ice cluster Insertion of the ice cluster in liquid water
Molecular Dynamics simulations at different temperatures
lead to bound the temperature at which the cluster is critical
Seeding technique to evaluate N*
Order parameter to detect the ice molecules
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Calculation of ∆µ: thermodynamic integration
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Calculation of the attachment rate f+
Perform a number of simulations of a cluster at the temperature at which the cluster is critical
f+ = slope/2
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Relevant results: Size of the critical cluster and nucleation rates
The size of the critical cluster is almost independent of the water model
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Size of the critical cluster and nucleation rates
The size of the cluster cluster seems to be independent of the
water model
E. Sanz et al., JACS 135, 15008 (2013)
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Size of the critical cluster and nucleation rates
The size of the cluster cluster seems to be independent of the
water model
It is impossible that liquid water nucleates homogeneously in Earth for a supercooling ∆T < 20 K
E. Sanz et al., JACS 135, 15008 (2013)
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Effect of salt on water anomalies (at extreme conditions)
Effect of salt on nucleation rate
Development of a force field for ionic solutions based on TIP4P/2005s
Ongoing work on NaCl solutions
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Université de Lyon
Gaël Pallares
Mouna El Mekki Azouzi
Frédéric Caupin
Carlos Vega
Eduardo Sanz
Chantal Valeriani
Miguel Angel González
Jorge Reñé
Pablo Rosales
Miguel Aníbal Portillo
Guiomar Delgado
Alberto Zaragoza
UCM team
Acknowledgements
We acknowledge the time allocated on the computational facilities
Minotauro and Tirant from the Spanish Supercomputing Network
(RES) along with the technical support.
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Supercooled TIP4P/2005 water: simulation vs. experiment
J.L.F.Abascal and C. Vega, JCP 134 186101 (2011)
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Iiquid-vapour spinodal
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A liquid-liquid critical point?
J.L.F. Abascal WaterSpain2013 - Zaragoza
J.L.F.Abascal and C. Vega , JCP 133, 234502 (2010)
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Parámetros de Orden