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ABSTRACT The homogeneous crystallization of water at low temperature is believed to occur through the direct nucleation of cubic (Ic) and hexagonal (Ih) ices. Here, we provide evidence from

molecular simulations that the nucleation of ice proceeds through the formation of a new metastable phase, which we name Ice 0. We find that Ice 0 is structurally similar to the supercooled

liquid, and that on growth it gradually converts into a stacking of Ice Ic and Ih. We suggest that this mechanism provides a thermodynamic explanation for the location and pressure

dependence of the homogeneous nucleation temperature, and that Ice 0 controls the homogeneous nucleation of low-pressure ices, acting as a precursor to crystallization in accordance with

Ostwald’s step rule of phases. Our findings show that metastable crystalline phases of water may play roles that have been largely overlooked. Access through your institution Buy or

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May 2023 REFERENCES * Eisenberg, D. & Kauzmann, W. _The Structure and Properties of Water_ (Oxford Univ. Press, 1969). Google Scholar  * Angell, C. A. Formation of glasses from liquids

and biopolymers. _Science_ 267, 1924–1935 (1995). Article  CAS  Google Scholar  * Mishima, O. & Stanley, H. The relationship between liquid, supercooled and glassy water. _Nature_ 396,

329–335 (1998). Article  CAS  Google Scholar  * Debenedetti, P. Supercooled and glassy water. _J. Phys. Condens. Matter_ 15, R1669–R1726 (2003). Article  CAS  Google Scholar  * Pruppacher,

H. R. A new look at homogeneous ice nucleation in supercooled water drops. _J. Atmos. Sci._ 52, 1924–1933 (1995). Article  Google Scholar  * Rosenfeld, D. & Woodley, W. L. Deep

convective clouds with sustained supercooled liquid water down to −37.5 °C. _Nature_ 405, 440–442 (2000). Article  CAS  Google Scholar  * Koop, T., Luo, B., Tsias, A. & Peter, T. Water

activity as the determinant for homogeneous ice nucleation in aqueous solutions. _Nature_ 406, 611–614 (2000). Article  CAS  Google Scholar  * Soper, A. K. Structural transformations in

amorphous ice and supercooled water and their relevance to the phase diagram of water. _Mol. Phys._ 106, 2053–2076 (2008). Article  CAS  Google Scholar  * Morishige, K. & Nobuoka, K.

X-ray diffraction studies of freezing and melting of water confined in a mesoporous adsorbent (MCM-41). _J. Chem. Phys._ 107, 6965–6969 (1997). Article  CAS  Google Scholar  * Jelassi, J. et

al. Studies of water and ice in hydrophilic and hydrophobic mesoporous silicas: pore characterisation and phase transformations. _Phys. Chem. Chem. Phys._ 12, 2838–2849 (2010). Article  CAS

  Google Scholar  * Hansen, T., Koza, M. & Kuhs, W. Formation and annealing of cubic ice: I. Modelling of stacking faults. _J. Phys. Condens. Matter_ 20, 285104 (2008). Article  Google

Scholar  * Shilling, J. et al. Measurements of the vapor pressure of cubic ice and their implications for atmospheric ice clouds. _Geophys. Res. Lett._ 33, L17801 (2006). Article  Google

Scholar  * Kobayashi, M. & Tanaka, H. Relationship between the phase diagram, the glass-forming ability, and the fragility of a water/salt mixture. _J. Phys. Chem. B_ 115, 14077–14090

(2011). Article  CAS  Google Scholar  * Mayer, E. & Hallbrucker, A. Cubic ice from liquid water. _Nature_ 325, 601–602 (1987). Article  CAS  Google Scholar  * Kohl, I., Mayer, E. &

Hallbrucker, A. The glassy water–cubic ice system: A comparative study by X-ray diffraction and differential scanning calorimetry. _Phys. Chem. Chem. Phys._ 2, 1579–1586 (2000). Article  CAS

  Google Scholar  * Murray, B. J. & Bertram, A. K. Formation and stability of cubic ice in water droplets. _Phys. Chem. Chem. Phys._ 8, 186–192 (2006). Article  CAS  Google Scholar  *

Malkin, T. L., Murray, B. J., Brukhno, A. V., Anwar, J. & Salzmann, C. G. Structure of ice crystallized from supercooled water. _Proc. Natl Acad. Sci. USA_ 109, 1041–1045 (2012). Article

  CAS  Google Scholar  * Svishchev, I. M. & Kusalik, P. G. Crystallization of liquid water in a molecular dynamics simulation. _Phys. Rev. Lett._ 73, 975–978 (1994). Article  CAS  Google

Scholar  * 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). Article

  CAS  Google Scholar  * Moore, E. B. & Molinero, V. Is it cubic? Ice crystallization from deeply supercooled water. _Phys. Chem. Chem. Phys._ 13, 20008–20016 (2011). Article  CAS 

Google Scholar  * Li, T., Donadio, D., Russo, G. & Galli, G. Homogeneous ice nucleation from supercooled water. _Phys. Chem. Chem. Phys._ 13, 19807–19813 (2011). Article  CAS  Google

Scholar  * Reinhardt, A., Doye, J. P., Noya, E. G. & Vega, C. Local order parameters for use in driving homogeneous ice nucleation with all-atom models of water. _J. Chem. Phys._ 137,

194504–194504 (2012). Article  Google Scholar  * Moore, E. & Molinero, V. Structural transformation in supercooled water controls the crystallization rate of ice. _Nature_ 479, 506–508

(2011). Article  CAS  Google Scholar  * Zhao, Z. et al. Tetragonal allotrope of group 14 elements. _J. Am. Chem. Soc._ 134, 12362–12365 (2012). Article  CAS  Google Scholar  * Abascal, J.

& Vega, C. A general purpose model for the condensed phases of water: TIP4P/2005. _J. Chem. Phys._ 123, 234505 (2005). Article  CAS  Google Scholar  * Sanz, E., Vega, C., Abascal, J.

& MacDowell, L. Phase diagram of water from computer simulation. _Phys. Rev. Lett._ 92, 255701 (2004). Article  CAS  Google Scholar  * Jacobson, L. C., Hujo, W. & Molinero, V.

Thermodynamic stability and growth of guest-free clathrate hydrates: a low-density crystal phase of water. _J. Phys. Chem. B_ 113, 10298–10307 (2009). Article  CAS  Google Scholar  * Romano,

F., Sanz, E. & Sciortino, F. Crystallization of tetrahedral patchy particles in silico. _J. Chem. Phys._ 134, 174502 (2011). Article  Google Scholar  * Ghiringhelli, L. M. et al.

State-of-the-art models for the phase diagram of carbon and diamond nucleation. _Mol. Phys._ 106, 2011–2038 (2008). Article  CAS  Google Scholar  * Ten Wolde, P. R., Ruiz-Montero, M. J.

& Frenkel, D. Numerical evidence for bcc ordering at the surface of a critical fcc nucleus. _Phys. Rev. Lett._ 75, 2714–2717 (1995). Article  CAS  Google Scholar  * Santra, M., Singh, R.

S. & Bagchi, B. Nucleation of a stable solid from melt in the presence of multiple metastable intermediate phases: Wetting, Ostwald step rule and vanishing polymorphs. _J. Phys. Chem.

B_ 117, 13154–13163 (2013). Article  CAS  Google Scholar  * Lundrigan, S. E. & Saika-Voivod, I. Test of classical nucleation theory and mean first-passage time formalism on

crystallization in the Lennard-Jones liquid. _J. Chem. Phys._ 131, 104503 (2009). Article  Google Scholar  * Sanz, E. et al. Homogeneous ice nucleation at moderate supercooling from

molecular simulation. _J. Am. Chem. Soc._ 135, 15008–15017 (2013). Article  CAS  Google Scholar  * Stillinger, F. H. Water revisited. _Science_ 209, 451–457 (1980). Article  CAS  Google

Scholar  * Russo, J. & Tanaka, H. Understanding water’s anomalies with locally favored structures. _Nature Commun._ 5, 3556 (2014). Article  Google Scholar  * Ghiringhelli, L. M.,

Valeriani, C., Meijer, E. & Frenkel, D. Local structure of liquid carbon controls diamond nucleation. _Phys. Rev. Lett._ 99, 055702 (2007). Article  CAS  Google Scholar  * Kawasaki, T.

& Tanaka, H. Formation of crystal nucleus from liquid. _Proc. Natl Acad. Sci. USA_ 107, 14036–14041 (2010). Article  CAS  Google Scholar  * Russo, J. & Tanaka, H. The microscopic

pathway to crystallization in supercooled liquids. _Sci. Rep._ 2, 505 (2012). Article  Google Scholar  * Russo, J. & Tanaka, H. Selection mechanism of polymorphs in the crystal

nucleation of the Gaussian core model. _Soft Matter_ 8, 4206–4215 (2012). Article  CAS  Google Scholar  * Tanaka, H. Bond orientational order in liquids: Towards a unified description of

water-like anomalies, liquid–liquid transition, glass transition, and crystallization. _Eur. Phys. J. E_ 35, 1–84 (2012). Article  CAS  Google Scholar  * Seidl, M., Amann-Winkel, K., Handle,

P. H., Zifferer, G. & Loerting, T. From parallel to single crystallization kinetics in high-density amorphous ice. _Phys. Rev. B_ 88, 174105 (2013). Article  Google Scholar  * Marchand,

D. J., Hsiao, E. & Kim, S. H. Non-contact AFM imaging in water using electrically-driven cantilever vibration. _Langmuir_ 29, 6762–6769 (2013). Article  CAS  Google Scholar  * Lied, A.,

Dosch, H. & Bilgram, J. H. Surface melting of ice I_h_ single crystals revealed by glancing angle X-ray scattering. _Phys. Rev. Lett._ 72, 3554–3557 (1994). Article  CAS  Google Scholar

  * Vega, C., Sanz, E., Abascal, J. & Noya, E. Determination of phase diagrams via computer simulation: Methodology and applications to water, electrolytes and proteins. _J. Phys.

Condens. Matter_ 20, 153101 (2008). Article  Google Scholar  * Steinhardt, P. J., Nelson, D. R. & Ronchetti, M. Bond-orientational order in liquids and glasses. _Phys. Rev. B_ 28,

784–805 (1983). Article  CAS  Google Scholar  * Lechner, W. & Dellago, C. Accurate determination of crystal structures based on averaged local bond order parameters. _J. Chem. Phys._

129, 114707 (2008). Article  Google Scholar  * Auer, S. & Frenkel, D. Prediction of absolute crystal-nucleation rate in hard-sphere colloids. _Nature_ 409, 1020–1023 (2001). Article  CAS

  Google Scholar  Download references ACKNOWLEDGEMENTS We are grateful to F. Sciortino for a critical reading of the manuscript and to J. Doye and A. Reinhardt for useful discussions. This

study was partly supported by Grants-in-Aid for Scientific Research (S) and Specially Promoted Research from the Japan Society for the Promotion of Science (JSPS), the Aihara Project, the

FIRST programme from JSPS, initiated by the Council for Science and Technology Policy (CSTP), a JSPS short-term fellowship for F.R., and a JSPS Postdoctoral Fellowship for J.R. AUTHOR

INFORMATION Author notes * John Russo and Flavio Romano: These authors contributed equally to this work. AUTHORS AND AFFILIATIONS * Institute of Industrial Science, University of Tokyo,

4-6-1 Komaba, Meguro-ku Tokyo 153-8505, Japan, John Russo, Flavio Romano & Hajime Tanaka * Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford,

South Parks Road Oxford OX1 3QZ, UK, Flavio Romano Authors * John Russo View author publications You can also search for this author inPubMed Google Scholar * Flavio Romano View author

publications You can also search for this author inPubMed Google Scholar * Hajime Tanaka View author publications You can also search for this author inPubMed Google Scholar CONTRIBUTIONS

J.R. and F.R. performed the numerical simulations and the data analysis. H.T. proposed and supervised the study. All authors discussed the results and contributed to the writing of the

manuscript. CORRESPONDING AUTHOR Correspondence to Hajime Tanaka. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing financial interests. SUPPLEMENTARY INFORMATION

SUPPLEMENTARY INFORMATION Supplementary Information (PDF 2172 kb) RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Russo, J., Romano, F. & Tanaka, H.

New metastable form of ice and its role in the homogeneous crystallization of water. _Nature Mater_ 13, 733–739 (2014). https://doi.org/10.1038/nmat3977 Download citation * Received: 22

September 2013 * Accepted: 08 April 2014 * Published: 18 May 2014 * Issue Date: July 2014 * DOI: https://doi.org/10.1038/nmat3977 SHARE THIS ARTICLE Anyone you share the following link with

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