DOI: 10.1073/pnas.0603253103. The violation of the Stokes–Einstein relation in supercooled water

The violation of the Stokes–Einstein relation in supercooled water

10.1073/pnas.0603253103

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

By confining water in nanopores, so narrow that the liquid cannot freeze, it is possible to explore its properties well below its homogeneous nucleation temperature T H ≈ 235 K. In particular, the dynamical parameters of water can be measured down to 180 K, approaching the suggested glass transition temperature T g ≈ 165 K. Here we present experimental evidence, obtained from Nuclear Magnetic Resonance and Quasi-Elastic Neutron Scattering spectroscopies, of a well defined decoupling of transport properties (the self-diffusion coefficient and the average translational relaxation time), which implies the breakdown of the Stokes–Einstein relation. We further show that such a non-monotonic decoupling reflects the characteristics of the recently observed dynamic crossover, at ≈225 K, between the two dynamical behaviors known as fragile and strong, which is a consequence of a change in the hydrogen bond structure of liquid water.

Bibliography

Chen, S.-H., Mallamace, F., Mou, C.-Y., Broccio, M., Corsaro, C., Faraone, A., & Liu, L. (2006). The violation of the StokesâEinstein relation in supercooled water. Proceedings of the National Academy of Sciences, 103(35), 12974â12978.

Authors 7

Sow-Hsin Chen (first)
Francesco Mallamace (additional)
Chung-Yuan Mou (additional)
Matteo Broccio (additional)
Carmelo Corsaro (additional)
Antonio Faraone (additional)
Li Liu (additional)

References 36 Referenced 287

C. A. Angell Water: A Comprehensive Treatise, ed F. Franks (Plenum, New York) Vol. 7, 1–81 (1982). / Water: A Comprehensive Treatise by Angell C. A. (1982)
10.1063/1.1595053
10.1038/24540
10.1126/science.1061757
10.1126/science.273.5282.1675
10.1088/0034-4885/55/3/001
C. A. Angell Complex Behavior of Glassy Systems, eds M. Rubí, C. Péres-Vicente (Springer, Berlin, 1997). / Complex Behavior of Glassy Systems by Angell C. A. (1997)
10.1126/science.267.5206.1924
10.1038/360324a0
10.1038/19042
10.1103/PhysRevLett.84.2881
10.1038/35002027
10.1038/35046035
10.1088/0953-8984/16/45/009
10.1016/S0301-0104(00)00208-1
10.1063/1.1832595
L. Liu, S.-H. Chen, A. Faraone, C.-W. Yen, C.-Y. Mou Phys. Rev. Lett. 95, 117802-1–117802-4 (2005). / Phys. Rev. Lett. by Liu L. (2005)
10.1073/pnas.0507870102
10.1146/annurev.physchem.51.1.99
10.1007/BF01323572
10.1103/PhysRevLett.90.015901
10.1002/cphc.200400610
10.1021/jp9640989
10.1063/1.471433
10.1021/jp004616m
10.1063/1.480752
10.1103/PhysRevE.69.061205
10.1103/PhysRevLett.81.4915
10.1016/S0167-2991(03)80444-5
10.1039/b010086m
10.1063/1.474936
10.1063/1.1568557
10.1016/S0301-0104(03)00124-1
10.1063/1.1695690
10.1002/(SICI)1099-0534(1998)10:4<197::AID-CMR1>3.0.CO;2-S
10.1063/1.2193159

Dates

Type	When
Created	19 years ago (Aug. 18, 2006, 8:34 p.m.)
Deposited	3 years, 4 months ago (April 12, 2022, 2:57 p.m.)
Indexed	2 weeks, 1 day ago (Aug. 6, 2025, 9:49 a.m.)
Issued	18 years, 11 months ago (Aug. 29, 2006)
Published	18 years, 11 months ago (Aug. 29, 2006)
Published Online	18 years, 11 months ago (Aug. 29, 2006)
Published Print	18 years, 11 months ago (Aug. 29, 2006)

Funders 0

None

BibTeX

@article{Chen_2006, title={The violation of the Stokes–Einstein relation in supercooled water}, volume={103}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.0603253103}, DOI={10.1073/pnas.0603253103}, number={35}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Chen, Sow-Hsin and Mallamace, Francesco and Mou, Chung-Yuan and Broccio, Matteo and Corsaro, Carmelo and Faraone, Antonio and Liu, Li}, year={2006}, month=aug, pages={12974–12978} }

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