DOI: 10.1073/pnas.1323366111. Anomalies in bulk supercooled water at negative pressure

Anomalies in bulk supercooled water at negative pressure

10.1073/pnas.1323366111

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

Significance Water is the most familiar liquid, and arguably the most complex. Anomalies of supercooled water have been measured during decades, and competing interpretations proposed. Yet, a decisive experiment remains elusive, because of unavoidable crystallization into ice. We investigate the state of water that is both supercooled and under mechanical tension, or negative pressure. Liquids under negative pressure can be found in plants or fluid inclusions in minerals. Using such water inclusions in quartz, we report, to our knowledge, the first measurements on doubly metastable water down to −15°C and around − 100 M P a . We observe sound velocity anomalies that can be reproduced quantitatively with molecular dynamics simulations. These results suggest the possibility to rule out two proposed scenarios for water anomalies, and put further constraints on the remaining ones.

Bibliography

Pallares, G., El Mekki Azouzi, M., GonzÃ¡lez, M. A., Aragones, J. L., Abascal, J. L. F., Valeriani, C., & Caupin, F. (2014). Anomalies in bulk supercooled water at negative pressure. Proceedings of the National Academy of Sciences, 111(22), 7936â7941.

Authors 7

Gaël Pallares (first)
Mouna El Mekki Azouzi (additional)
Miguel A. González (additional)
Juan L. Aragones (additional)
José L. F. Abascal (additional)
Chantal Valeriani (additional)
Frédéric Caupin (additional)

References 56 Referenced 115

10.1063/1.433153
10.1021/j100395a030
; The International Association for the Properties of Water and Steam Revised release on the IAPWS formulation 1995 for the thermodynamic properties of ordinary water substance for general and scientific use. Available at www.iapws.org/relguide/IAPWS-95.html. Accessed October 20 2013. (2009).
10.1038/360324a0
F Sciortino, PH Poole, U Essmann, HE Stanley, Line of compressibility maxima in the phase diagram of supercooled water. Phys Rev E Stat Phys Plasmas Fluids Relat Interdiscip Topics 55, 727–737 (1997). / Phys Rev E Stat Phys Plasmas Fluids Relat Interdiscip Topics / Line of compressibility maxima in the phase diagram of supercooled water by Sciortino F (1997)
10.1073/pnas.0507870102
10.1038/nphys2475
10.1088/0953-8984/15/45/R01
10.1103/PhysRevLett.73.1632
Q Zheng, et al. Liquids Under Negative Pressure, NATO Science Series II, eds AR Imre, HJ Maris, PR Williams (Kluwer Academic Publishers, Dordrecht, The Netherlands) Vol 84, 33–46 (2002). (10.1007/978-94-010-0498-5_4) / Liquids Under Negative Pressure, NATO Science Series II by Zheng Q (2002)
10.1126/science.1131939
10.1103/PhysRevE.53.6144
10.1073/pnas.0912756107
10.1073/pnas.0701352104
10.1038/nmat3271
10.1016/j.crhy.2006.10.015
10.1002/9781118540350.ch3
10.1126/science.254.5033.829
10.1063/1.464497
10.1016/j.gca.2009.02.006
10.1088/0022-3735/13/7/019
10.1051/jphyslet:0197800390708300
10.1051/jphys:01980004109099700
10.1063/1.443413
10.1103/PhysRevLett.52.1025
10.1021/j100339a077
10.1063/1.472263
10.1063/1.3495971
10.1063/1.1376424
10.1103/PhysRevLett.88.195701
10.1063/1.2121687
10.1039/c1cp22168j
10.1063/1.3585676
10.1063/1.2215612
10.1063/1.453710
10.1039/b101773j
10.1063/1.3506860
10.1063/1.4807479
10.1126/science.189.4206.880
10.1038/24540
; The International Association for the Properties of Water and Steam Revised supplementary release: Saturation properties of ordinary water substance September 1992. Available at http://www.iapws.org/relguide/supsat.pdf. Accessed October 20 2013. (1992).
JP Boon, S Yip Molecular Hydrodynamics (McGraw-Hill, New York, 1980). / Molecular Hydrodynamics by Boon JP (1980)
; The International Association for the Properties of Water and Steam Release on the refractive index of ordinary water substance as a function of wavelength temperature and pressure. Available at http://www.iapws.org/relguide/rindex.pdf. Accessed October 20 2013. (1997).
10.1063/1.3243314
10.1063/1.3156856
10.1063/1.3182727
10.1103/PhysRevLett.107.155702
10.1039/B805531A
10.1021/jp105975c
10.1021/ct700301q
10.1002/jcc.20291
10.1063/1.470117
10.1021/ct700200b
10.1063/1.2408420
10.1063/1.328693
10.1063/1.4737867

Dates

Type	When
Created	11 years, 3 months ago (May 19, 2014, 10:36 p.m.)
Deposited	3 years, 4 months ago (April 12, 2022, 10:49 p.m.)
Indexed	2 weeks, 3 days ago (Aug. 6, 2025, 9:32 a.m.)
Issued	11 years, 3 months ago (May 19, 2014)
Published	11 years, 3 months ago (May 19, 2014)
Published Online	11 years, 3 months ago (May 19, 2014)
Published Print	11 years, 2 months ago (June 3, 2014)

Funders 0

None

BibTeX

@article{Pallares_2014, title={Anomalies in bulk supercooled water at negative pressure}, volume={111}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.1323366111}, DOI={10.1073/pnas.1323366111}, number={22}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Pallares, Gaël and El Mekki Azouzi, Mouna and González, Miguel A. and Aragones, Juan L. and Abascal, José L. F. and Valeriani, Chantal and Caupin, Frédéric}, year={2014}, month=may, pages={7936–7941} }

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