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Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature

Abstract

Water has a number of anomalous physical properties, and some of these become drastically enhanced on supercooling below the freezing point. Particular interest has focused on thermodynamic response functions that can be described using a normal component and an anomalous component that seems to diverge at about 228 kelvin (refs 1,2,3 ). This has prompted debate about conflicting theories4,5,6,7,8,9,10,11,12 that aim to explain many of the anomalous thermodynamic properties of water. One popular theory attributes the divergence to a phase transition between two forms of liquid water occurring in the ‘no man’s land’ that lies below the homogeneous ice nucleation temperature (TH) at approximately 232 kelvin13 and above about 160 kelvin14, and where rapid ice crystallization has prevented any measurements of the bulk liquid phase. In fact, the reliable determination of the structure of liquid water typically requires temperatures above about 250 kelvin2,15. Water crystallization has been inhibited by using nanoconfinement16, nanodroplets17 and association with biomolecules16 to give liquid samples at temperatures below TH, but such measurements rely on nanoscopic volumes of water where the interaction with the confining surfaces makes the relevance to bulk water unclear18. Here we demonstrate that femtosecond X-ray laser pulses can be used to probe the structure of liquid water in micrometre-sized droplets that have been evaporatively cooled19,20,21 below TH. We find experimental evidence for the existence of metastable bulk liquid water down to temperatures of  kelvin in the previously largely unexplored no man’s land. We observe a continuous and accelerating increase in structural ordering on supercooling to approximately 229 kelvin, where the number of droplets containing ice crystals increases rapidly. But a few droplets remain liquid for about a millisecond even at this temperature. The hope now is that these observations and our detailed structural data will help identify those theories that best describe and explain the behaviour of water.

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Figure 1: Coherent X-ray scattering from individual micrometre-sized droplets with a single-shot selection scheme.
Figure 2: Time dependence of water crystallization during evaporative cooling.
Figure 3: Temperature dependence of water scattering peaks.
Figure 4: Temperature dependence of the tetrahedrality of liquid water.

References

  1. Speedy, R. J. & Angell, C. A. Isothermal compressibility of supercooled water and evidence for a thermodynamic singularity at −45°C. J. Chem. Phys. 65, 851–858 (1976)

    CAS  Article  ADS  Google Scholar 

  2. Huang, C. et al. Increasing correlation length in bulk supercooled H2O, D2O, and NaCl solution determined from small angle X-ray scattering. J. Chem. Phys. 133, 134504 (2010)

    Article  ADS  Google Scholar 

  3. Angell, C. A., Sichina, W. J. & Oguni, M. Heat capacity of water at extremes of supercooling and superheating. J. Phys. Chem. 86, 998–1002 (1982)

    CAS  Article  Google Scholar 

  4. Poole, P. H., Sciortino, F., Essmann, U. & Stanley, H. E. Phase behaviour of metastable water. Nature 360, 324–328 (1992)

    CAS  Article  ADS  Google Scholar 

  5. Sastry, S., Debenedetti, P. G., Sciortino, F. & Stanley, H. E. Singularity-free interpretation of the thermodynamics of supercooled water. Phys. Rev. E 53, 6144–6154 (1996)

    CAS  Article  ADS  Google Scholar 

  6. Angell, C. A. Insights into phases of liquid water from study of its unusual glass-forming properties. Science 319, 582–587 (2008)

    CAS  Article  Google Scholar 

  7. Limmer, D. T. & Chandler, D. The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water. J. Chem. Phys. 135, 134503 (2011)

    Article  ADS  Google Scholar 

  8. Palmer, J. C., Car, R. & Debenedetti, P. G. The liquid-liquid transition in supercooled ST2 water: a comparison between umbrella sampling and well-tempered metadynamics. Faraday Discuss. 167, 77–94 (2013)

    Article  ADS  Google Scholar 

  9. Speedy, R. J. Stability-limit conjecture. An interpretation of the properties of water. J. Phys. Chem. 86, 982–991 (1982)

    CAS  Article  Google Scholar 

  10. Moore, E. B. & Molinero, V. Structural transformation in supercooled water controls the crystallization rate of ice. Nature 479, 506–508 (2011)

    CAS  Article  ADS  Google Scholar 

  11. Holten, V. & Anisimov, M. A. Entropy-driven liquid–liquid separation in supercooled water. Sci. Rep. 2, 713 (2012)

    CAS  Article  ADS  Google Scholar 

  12. Overduin, S. D. & Patey, G. N. An analysis of fluctuations in supercooled TIP4P/2005 water. J. Chem. Phys. 138, 184502 (2013)

    CAS  Article  ADS  Google Scholar 

  13. Mason, B. J. The supercooling and nucleation of water. Adv. Phys. 7, 221–234 (1958)

    CAS  Article  ADS  Google Scholar 

  14. Smith, R. S. & Kay, B. D. The existence of supercooled liquid water at 150 K. Nature 398, 788–791 (1999)

    CAS  Article  ADS  Google Scholar 

  15. Neuefeind, J., Benmore, C. J., Weber, J. K. R. & Paschek, D. More accurate X-ray scattering data of deeply supercooled bulk liquid water. Mol. Phys. 109, 279–288 (2011)

    CAS  Article  ADS  Google Scholar 

  16. Mallamace, F., Corsaro, C., Baglioni, P., Fratini, E. & Chen, S.-H. The dynamical crossover phenomenon in bulk water, confined water and protein hydration water. J. Phys. Condens. Matter 24, 064103 (2012)

    Article  ADS  Google Scholar 

  17. Manka, A. et al. Freezing water in no-man’s land. Phys. Chem. Chem. Phys. 14, 4505–4516 (2012)

    CAS  Article  Google Scholar 

  18. Levinger, N. E. Water in confinement. Science 298, 1722–1723 (2002)

    CAS  Article  Google Scholar 

  19. Faubel, M., Schlemmer, S. & Toennies, J. P. A molecular beam study of the evaporation of water from a liquid jet. Z. Phys. D 10, 269–277 (1988)

    CAS  Article  ADS  Google Scholar 

  20. Rayleigh, F. R. S. On the instability of jets. Proc. Lond. Math. Soc. 10, 4–12 (1879)

    MathSciNet  MATH  Google Scholar 

  21. DePonte, D. P. et al. Gas dynamic virtual nozzle for generation of microscopic droplet streams. J. Phys. D Appl. Phys. 41, 195505 (2008)

    Article  ADS  Google Scholar 

  22. Bowron, D. T. et al. The local and intermediate range structures of the five amorphous ices at 80 K and ambient pressure: a Faber-Ziman and Bhatia-Thornton analysis. J. Chem. Phys. 125, 194502 (2006)

    CAS  Article  ADS  Google Scholar 

  23. Tulk, C. A. et al. Structural studies of several distinct metastable forms of amorphous ice. Science 297, 1320–1323 (2002)

    CAS  Article  ADS  Google Scholar 

  24. Skinner, L. B. et al. Benchmark oxygen-oxygen pair-distribution function of ambient water from x-ray diffraction measurements with a wide Q-range. J. Chem. Phys. 138, 074506 (2013)

    Article  ADS  Google Scholar 

  25. Okhulkov, A. V., Demianets, Y. N. & Gorbaty, Y. E. X-ray scattering in liquid water at pressures of up to 7.7 kbar: test of a fluctuation model. J. Chem. Phys. 100, 1578–1588 (1994)

    CAS  Article  ADS  Google Scholar 

  26. Narten, A. H., Danford, M. D. & Levy, H. A. X-ray diffraction study of liquid water in temperature range 4–200 °C. Discuss. Faraday Soc. 43, 97–107 (1967)

    Article  Google Scholar 

  27. Errington, J. R. & Debenedetti, P. G. Relationship between structural order and the anomalies of liquid water. Nature 409, 318–321 (2001)

    CAS  Article  ADS  Google Scholar 

  28. Matsumoto, M., Saito, S. & Ohmine, I. Molecular dynamics simulation of the ice nucleation and growth process leading to water freezing. Nature 416, 409–413 (2002)

    CAS  Article  ADS  Google Scholar 

  29. Boutet, S. & Williams, G. J. The coherent X-ray imaging (CXI) instrument at the Linac Coherent Light Source (LCLS). New J. Phys. 12, 035024 (2010)

    Article  ADS  Google Scholar 

  30. Wikfeldt, K. T., Huang, C., Nilsson, A. & Pettersson, L. G. M. Enhanced small-angle scattering connected to the Widom line in simulations of supercooled water. J. Chem. Phys. 134, 214506 (2011)

    CAS  Article  ADS  Google Scholar 

Download references

Acknowledgements

We acknowledge the US Department of Energy (DOE) through the SLAC Laboratory Directed Research and Development Program, Office of Basic Energy Sciences through SSRL and LCLS; the AMOS programme within the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Sciences; and the Swedish Research Council for financial support. The molecular dynamics simulations were performed on resources provided by the Swedish National Infrastructure for Computing at the NSC and HPC2N centres. Parts of this research were carried out at LCLS at the SLAC National Accelerator Laboratory. LCLS is an Office of Science User Facility operated for the DOE Office of Science by Stanford University. We also acknowledge the support of the SSRL Structural Molecular Biology group funded by the National Institutes of Health, National Center for Research Resources, Biomedical Technology Grant and the US Department of Energy, Office of Biological and Environmental Research. We wish to thank D. Schafer and M. Hayes for mechanical support; W. Ghonsalves and F. Hoeflich for software support; the SLAC detector group for assistance with the Cornell-SLAC pixel array detector; H. Nakatsutsumi, K. Beyerlein and C. Gati for nozzle support; D. Bowron for providing the data files from ref. 22; J. Spence and C. Stan for discussions; and H. E. Stanley, V. Molinero, C. A. Angell and D. Chandler for critical reading of the manuscript.

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Contributions

A.N., C.H. and M.J.B. had the idea for and designed the experiment; S.B., G.J.W., M.M. and M.M.S. operated the coherent X-ray imaging instrument; M.J.B., D.P.D., T.A.M., J.A.S., C.H., R.G.S., C.Y.H., H.L. and D. Starodub developed, tested and ran the sample delivery system; C.H., T.A.M. and T.M.W. performed the SSRL experiment; J.A.S., T.A.M., H.L., R.G.S., C.H., D.N., M.B., D.P.D., D. Starodub, C.Y.H., C. Chen, L.B.S., M.M.S., M.M., G.J.W., S.B., M.J.B. and A.N. performed the LCLS experiments; A.B., J.A.S., N.D.L., A.V.M., G.J.W. and C. Caronna developed data processing software; J.A.S., C.H., N.D.L., H.L., D.N., A.V.M. and J.F. processed, sorted and analysed data; D. Schlesinger, K.T.W. and L.G.M.P. designed and performed the molecular dynamics simulations; D. Schlesinger, J.A.S., C.H., T.A.M., D. Starodub and L.G.M.P. implemented and simulated the Knudsen theory of evaporation; and A.N., C.H., L.G.M.P., J.A.S., D. Schlesinger and N.D.L. wrote the manuscript with input from all authors.

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Correspondence to J. A. Sellberg or A. Nilsson.

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Extended data figures and tables

Extended Data Table 1 Temperature-dependent S1 and S2 peak positions for the 5-µl static sample
Extended Data Table 2 Temperature-dependent S1 and S2 peak positions for the 34–37-µm-diameter droplets
Extended Data Table 3 Temperature-dependent S1 and S2 peak positions for the 12-µm-diameter droplets
Extended Data Table 4 Temperature-dependent S1 and S2 peak positions for the 9-µm-diameter droplets

Supplementary information

Supplementary Information

This file contains Supplementary Text, Supplementary Figures 1-22, Supplementary Tables 1-6 and Supplementary References. (PDF 8612 kb)

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Sellberg, J., Huang, C., McQueen, T. et al. Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature. Nature 510, 381–384 (2014). https://doi.org/10.1038/nature13266

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