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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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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  1. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, USA

    • J. A. Sellberg
    • , T. A. McQueen
    • , M. Beye
    • , C. Chen
    •  & A. Nilsson
  2. Department of Physics, AlbaNova University Center, Stockholm University, S-106 91 Stockholm, Sweden

    • J. A. Sellberg
    • , D. Schlesinger
    • , K. T. Wikfeldt
    • , L. G. M. Pettersson
    •  & A. Nilsson
  3. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, PO Box 20450, Stanford, California 94309, USA

    • C. Huang
    • , D. Nordlund
    • , T. M. Weiss
    •  & A. Nilsson
  4. Department of Chemistry, Stanford University, Stanford, California 94305, USA

    • T. A. McQueen
    •  & C. Chen
  5. PULSE Institute, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, USA

    • N. D. Loh
    • , H. Laksmono
    • , R. G. Sierra
    • , C. Y. Hampton
    • , D. Starodub
    •  & M. J. Bogan
  6. Center for Free-Electron Laser Science, DESY, Notkestrasse 85, 22607 Hamburg, Germany

    • D. P. DePonte
    • , A. V. Martin
    •  & A. Barty
  7. Linac Coherent Light Source, SLAC National Accelerator Laboratory, PO Box 20450, Stanford, California 94309, USA

    • D. P. DePonte
    • , C. Caronna
    • , J. Feldkamp
    • , M. M. Seibert
    • , M. Messerschmidt
    • , G. J. Williams
    •  & S. Boutet
  8. Institute for Methods and Instrumentation in Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Wilhelm-Conrad-Röntgen Campus, Albert-Einstein-Strasse 15, 12489 Berlin, Germany

    • M. Beye
  9. Mineral Physics Institute, Stony Brook University, Stony Brook, New York, New York 11794-2100, USA

    • L. B. Skinner


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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.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

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

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    This file contains Supplementary Text, Supplementary Figures 1-22, Supplementary Tables 1-6 and Supplementary References.

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