Abstract
Using electron spin resonance spectroscopy (ESR), we measure the rotational mobility of probe molecules highly diluted in deeply supercooled bulk water and negligibly constrained by the possible ice fraction. The mobility increases above the putative glass transition temperature of water, T g = 136 K, and smoothly connects to the thermodynamically stable region by traversing the so called “no man's land” (the range 150–235 K), where it is believed that the homogeneous nucleation of ice suppresses the liquid water. Two coexisting fractions of the probe molecules are evidenced. The 2 fractions exhibit different mobility and fragility; the slower one is thermally activated (low fragility) and is larger at low temperatures below a fragile-to-strong dynamic cross-over at ≈225 K. The reorientation of the probe molecules decouples from the viscosity below ≈225 K. The translational diffusion of water exhibits a corresponding decoupling at the same temperature [Chen S-H, et al. (2006) The violation of the Stokes–Einstein relation in supercooled water. Proc Natl Acad Sci USA 103:12974–12978]. The present findings are consistent with key issues concerning both the statics and the dynamics of supercooled water, namely the large structural fluctuations [Poole PH, Sciortino F, Essmann U, Stanley HE (1992) Phase behavior of metastable water. Nature 360:324–328] and the fragile-to-strong dynamic cross-over at ≈228 K [Ito K, Moynihan CT, Angell CA (1999) Thermodynamic determination of fragility in liquids and a fragile-to-strong liquid transition in water. Nature 398:492–494].
References
45
Referenced
70
10.1038/24540
10.1088/0953-8984/15/45/R01
10.1126/science.1131939
10.1038/19725
10.1021/jp980765h
10.1038/19042
- W Rosenhain, D Ewen, The intercrystalline cohesion of metals. J Inst Metals 10, 119–148 (1913). / J Inst Metals / The intercrystalline cohesion of metals by Rosenhain W (1913)
10.1038/1881144a0
10.1063/1.474468
10.1021/jp0672050
10.1063/1.476649
10.1017/S0022143000002240
10.1063/1.1695859
10.1021/j100679a003
10.1038/331247a0
10.1017/S0022143000005839
10.1146/annurev.fluid.37.061903.175758
10.1073/pnas.0603253103
10.1073/pnas.0607138104
10.1073/pnas.0706504104
10.1073/pnas.0507870102
10.1103/PhysRevLett.95.117802
10.1038/360324a0
10.1103/PhysRevE.54.6331
10.1038/nature02409
10.1073/pnas.0702608104
10.1103/PhysRevLett.97.055901
10.1103/PhysRevE.76.031203
10.1038/35053024
10.1126/science.1122154
10.1209/epl/i1997-00301-2
-
C De Michele, D Leporini, Viscous flow and jump dynamics in molecular supercooled liquids. II. Rotations. Phys Rev E 63, 036702–036710. (2001).
(
10.1103/PhysRevE.63.036702
) / Phys Rev E / Viscous flow and jump dynamics in molecular supercooled liquids. II. Rotations by De Michele C (2001) 10.1002/0470084987
10.1016/B978-0-12-092350-2.50007-2
10.1103/PhysRevA.28.2474
10.1103/PhysRevLett.95.235702
10.1063/1.1679640
10.1088/0953-8984/8/21/007
10.1016/S0378-4371(03)00012-8
10.6028/jres.102.013
10.1038/35018034
10.1073/pnas.0805032105
10.1021/ja991961k
10.1007/BF03162503
10.1073/pnas.0900227106
Dates
Type | When |
---|---|
Created | 16 years, 2 months ago (June 25, 2009, 9:59 p.m.) |
Deposited | 3 years, 4 months ago (April 12, 2022, 5:29 p.m.) |
Indexed | 1 month ago (July 30, 2025, 11:12 a.m.) |
Issued | 16 years, 1 month ago (July 14, 2009) |
Published | 16 years, 1 month ago (July 14, 2009) |
Published Online | 16 years, 1 month ago (July 14, 2009) |
Published Print | 16 years, 1 month ago (July 14, 2009) |
@article{Banerjee_2009, title={ESR evidence for 2 coexisting liquid phases in deeply supercooled bulk water}, volume={106}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.0900734106}, DOI={10.1073/pnas.0900734106}, number={28}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Banerjee, D. and Bhat, S. N. and Bhat, S. V. and Leporini, D.}, year={2009}, month=jul, pages={11448–11453} }