P. Mazur, Cryobiology: The Freezing of Biological Systems, Science, vol.168, issue.3934, pp.939-949, 1970.
DOI : 10.1126/science.168.3934.939

J. Sevigny, The antibody aducanumab reduces A?? plaques in Alzheimer???s disease, Nature, vol.94, issue.7618, pp.50-56, 2016.
DOI : 10.1073/pnas.94.4.1550

J. R. Cox, L. A. Ferris, and V. R. Thalladi, Selective Growth of a Stable Drug Polymorph by Suppressing the Nucleation of Corresponding Metastable Polymorphs, Angewandte Chemie International Edition, vol.7, issue.23, pp.4333-4336, 2007.
DOI : 10.1248/cpb.34.1784

S. L. Price, Predicting crystal structures of organic compounds, Chem. Soc. Rev., vol.19, issue.7, pp.2098-2111, 2014.
DOI : 10.1002/chem.201204369

J. D. Atkinson, The importance of feldspar for ice nucleation by mineral dust in mixed-phase clouds, Nature, vol.6, issue.7454, pp.355-358, 2013.
DOI : 10.5194/acp-6-4321-2006

T. W. Wilson, A marine biogenic source of atmospheric ice-nucleating particles, Nature, vol.12, issue.7568, pp.234-238, 2015.
DOI : 10.5194/acp-12-845-2012

A. Jain, Commentary: The Materials Project: A materials genome approach to accelerating materials innovation, APL Materials, vol.2, issue.1, p.11002, 2013.
DOI : 10.1016/j.jmmm.2013.04.025

M. Volmer and A. Weber, Particle formation and particle action as a special case of heterogeneous catalysis, Z. Elektrochem. Angew. Phys. Chem, vol.35, pp.555-561, 1929.

D. Turnbull, Kinetics of Heterogeneous Nucleation, The Journal of Chemical Physics, vol.29, issue.2, pp.198-203, 1950.
DOI : 10.1063/1.1698534

T. Bartels-rausch, Chemistry: Ten things we need to know about ice and snow, Nature, vol.12, issue.7435, pp.27-29, 2013.
DOI : 10.5194/acpd-12-30409-2012

G. C. Sosso, Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations, Chemical Reviews, vol.116, issue.12, pp.7078-7116, 2016.
DOI : 10.1021/acs.chemrev.5b00744

S. Chung, Y. Kim, J. Kim, and Y. Kim, Multiphase transformation and Ostwald???s rule of stages during crystallization of??a??metal phosphate, Nature Physics, vol.100, issue.1, pp.68-73, 2009.
DOI : 10.1557/mrs2004.266

E. M. Pouget, The Initial Stages of Template-Controlled CaCO3 Formation Revealed by Cryo-TEM, Science, vol.87, issue.5610, pp.1455-1458, 2009.
DOI : 10.1126/science.1079204

M. Sleutel, J. Lutsko, A. E. Van-driessche, M. A. Durán-olivencia, and D. Maes, Observing classical nucleation theory at work by monitoring phase transitions with molecular precision, Nature Communications, vol.10, p.5598, 2014.
DOI : 10.2478/s11534-011-0096-2

J. A. Sellberg, Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature, Nature, vol.134, issue.7505, pp.381-384, 2014.
DOI : 10.1063/1.3594545

E. B. Moore and V. Molinero, Structural transformation in supercooled water controls the crystallization rate of ice, Nature, vol.113, issue.7374, pp.506-508, 2011.
DOI : 10.1021/jp903439a

S. Auer and D. Frenkel, Line Tension Controls Wall-Induced Crystal Nucleation in Hard-Sphere Colloids, Physical Review Letters, vol.57, issue.1, p.15703, 2003.
DOI : 10.1063/1.1678576

URL : https://dspace.library.uu.nl/bitstream/1874/10830/1/frenkel_03_line_wall-induced_crystal.pdf

T. Li, D. Donadio, and G. Galli, Ice nucleation at the nanoscale probes no man???s land of water, Nature Communications, vol.131, p.1887, 2013.
DOI : 10.1063/1.3268346

A. J. Page and R. P. Sear, Crystallization Controlled by the Geometry of a Surface, Journal of the American Chemical Society, vol.131, issue.48, pp.17550-17551, 2009.
DOI : 10.1021/ja9085512

A. J. Page and R. P. Sear, Heterogeneous Nucleation in and out of Pores, Physical Review Letters, vol.97, issue.6, p.65701, 2006.
DOI : 10.1063/1.1747588

J. A. Van-meel, R. P. Sear, and D. Frenkel, Design Principles for Broad-Spectrum Protein-Crystal Nucleants with Nanoscale Pits, Physical Review Letters, vol.105, issue.20, p.205501, 2010.
DOI : 10.1088/0953-8984/14/14/302

N. E. Chayen, E. Saridakis, and R. P. Sear, Experiment and theory for heterogeneous nucleation of protein crystals in a porous medium, Proc. Natl Acad. Sci. USA 103, pp.597-601, 2006.
DOI : 10.1016/S1047-8477(02)00609-3

M. Fitzner, G. C. Sosso, S. J. Cox, and A. Michaelides, The Many Faces of Heterogeneous Ice Nucleation: Interplay Between Surface Morphology and Hydrophobicity, Journal of the American Chemical Society, vol.137, issue.42, pp.13658-13669, 2015.
DOI : 10.1021/jacs.5b08748

A. J. Bourque, C. R. Locker, and G. C. Rutledge, Heterogeneous Nucleation of an n-Alkane on Tetrahedrally Coordinated Crystals, The Journal of Physical Chemistry B, vol.121, issue.4, pp.904-911, 2017.
DOI : 10.1021/acs.jpcb.6b12590

Y. Qiu and V. Molinero, Strength of Alkane???Fluid Attraction Determines the Interfacial Orientation of Liquid Alkanes and Their Crystallization through Heterogeneous or Homogeneous Mechanisms, Crystals, vol.2, issue.3, p.86, 2017.
DOI : 10.1063/1.1429645

Y. Bi, B. Cao, and T. Li, Enhanced heterogeneous ice nucleation by special surface geometry, Nature Communications, vol.22, p.15372, 2017.
DOI : 10.1063/1.2198827

URL : http://www.nature.com/articles/ncomms15372.pdf

P. Pedevilla, M. Fitzner, and A. Michaelides, What makes a good descriptor for heterogeneous ice nucleation on OH-patterned surfaces, Physical Review B, vol.96, issue.11, p.115441, 2017.
DOI : 10.1063/1.463940

R. P. Sear, The non-classical nucleation of crystals: microscopic mechanisms and applications to molecular crystals, ice and calcium carbonate, International Materials Reviews, vol.111, issue.6, pp.328-356, 2012.
DOI : 10.1002/aic.690490221

M. Volmer and A. Weber, Keimbildung in übersättigten gebilden, Z. Phys. Chem, vol.119, pp.277-301, 1926.
DOI : 10.1515/zpch-1926-11927

R. Becker and W. Döring, Kinetische Behandlung der Keimbildung in ??bers??ttigten D??mpfen, Annalen der Physik, vol.163, issue.8, pp.719-752, 1935.
DOI : 10.1002/andp.19354160806

J. Mithen and R. Sear, Computer simulation of epitaxial nucleation of a crystal on a crystalline surface, The Journal of Chemical Physics, vol.51, issue.8, p.84504, 2014.
DOI : 10.1103/PhysRevB.19.5299

S. Jung, M. K. Tiwari, N. V. Doan, and D. Poulikakos, Mechanism of supercooled droplet freezing on surfaces, Nature Communications, vol.336, p.615, 2012.
DOI : 10.1017/S0022112096004788

Y. Shibuta, Heterogeneity in homogeneous nucleation from billion-atom molecular dynamics simulation of solidification of pure metal, Nature Communications, vol.18, issue.1, p.10, 2017.
DOI : 10.1088/0965-0393/18/1/015012

G. C. Sosso, T. Li, D. Donadio, G. A. Tribello, and A. Michaelides, Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite, The Journal of Physical Chemistry Letters, vol.7, issue.13, pp.2350-2355, 2016.
DOI : 10.1021/acs.jpclett.6b01013

Y. Bi, R. Cabriolu, and T. Li, Heterogeneous Ice Nucleation Controlled by the Coupling of Surface Crystallinity and Surface Hydrophilicity, The Journal of Physical Chemistry C, vol.120, issue.3, pp.1507-1514, 2016.
DOI : 10.1021/acs.jpcc.5b09740

C. Hoose, J. E. Kristjánsson, J. Chen, and A. Hazra, A Classical-Theory-Based Parameterization of Heterogeneous Ice Nucleation by Mineral Dust, Soot, and Biological Particles in a Global Climate Model, Journal of the Atmospheric Sciences, vol.67, issue.8, pp.2483-2503, 2010.
DOI : 10.1175/2010JAS3425.1

S. Broadley, Immersion mode heterogeneous ice nucleation by an illite rich powder representative of atmospheric mineral dust, Atmospheric Chemistry and Physics, vol.12, issue.1, pp.287-307, 2012.
DOI : 10.5194/acp-12-287-2012

T. Li, D. Donadio, G. Russo, and G. Galli, Homogeneous ice nucleation from supercooled water, Physical Chemistry Chemical Physics, vol.105, issue.44, pp.19807-19813, 2011.
DOI : 10.1073/pnas.0707917105

L. Lupi, A. Hudait, and V. Molinero, Heterogeneous Nucleation of Ice on Carbon Surfaces, Journal of the American Chemical Society, vol.136, issue.8, pp.3156-3164, 2014.
DOI : 10.1021/ja411507a

R. Cabriolu and T. Li, Ice nucleation on carbon surface supports the classical theory for heterogeneous nucleation, Physical Review E, vol.119, issue.5, p.52402, 2015.
DOI : 10.1063/1.2409924

E. B. Moore and V. Molinero, Is it cubic? Ice crystallization from deeply supercooled water, Physical Chemistry Chemical Physics, vol.115, issue.44, pp.20008-20016, 2011.
DOI : 10.1021/jp110297q

A. Haji-akbari and P. G. Debenedetti, Direct calculation of ice homogeneous nucleation rate for a molecular model of water, Proc. Natl Acad. Sci. USA, pp.10582-10588, 2015.
DOI : 10.1063/1.2776270

D. Winter, P. Virnau, and K. Binder, Monte??Carlo Test of the Classical Theory for Heterogeneous Nucleation Barriers, Physical Review Letters, vol.119, issue.22, p.225703, 2009.
DOI : 10.1209/0295-5075/80/66002

V. K. Srirambhatla, R. Guo, S. L. Price, and A. J. Florence, Isomorphous template induced crystallisation: a robust method for the targeted crystallisation of computationally predicted metastable polymorphs, Chemical Communications, vol.10, issue.5???6, pp.7384-7386, 2016.
DOI : 10.1039/B712547J

H. I. Hauge, Hexagonal Silicon Realized, Nano Letters, vol.15, issue.9, pp.5855-5860, 2015.
DOI : 10.1021/acs.nanolett.5b01939

I. Levin and D. Brandon, Metastable Alumina Polymorphs: Crystal Structures and Transition Sequences, Journal of the American Ceramic Society, vol.44, issue.5, pp.1995-2012, 1998.
DOI : 10.1016/1359-6454(95)00265-0

S. E. Donnelly, Ordering in a Fluid Inert Gas Confined by Flat Surfaces, Science, vol.296, issue.5567, pp.507-510, 2002.
DOI : 10.1126/science.1068521

S. Ueno, Y. Hamada, and K. Sato, -Alkane Crystals in Emulsion Droplets through Interfacial Heterogeneous Nucleation, Crystal Growth & Design, vol.3, issue.6, pp.935-939, 2003.
DOI : 10.1021/cg0300230

A. Hudait, S. Qiu, L. Lupi, and V. Molinero, Free energy contributions and structural characterization of stacking disordered ices, Physical Chemistry Chemical Physics, vol.127, issue.14, pp.9544-9553, 2016.
DOI : 10.1021/ja056072d

A. Hudait and V. Molinero, What Determines the Ice Polymorph in Clouds?, Journal of the American Chemical Society, vol.138, issue.28, pp.8958-8967, 2016.
DOI : 10.1021/jacs.6b05227

Y. Bi, A. Porras, and T. Li, Free energy landscape and molecular pathways of gas hydrate nucleation, The Journal of Chemical Physics, vol.145, issue.21, p.211909, 2016.
DOI : 10.1038/ncomms6598

L. Lupi, B. Peters, and V. Molinero, Pre-ordering of interfacial water in the pathway of heterogeneous ice nucleation does not lead to a two-step crystallization mechanism, The Journal of Chemical Physics, vol.145, issue.21, p.211910, 2016.
DOI : 10.5194/amt-8-3519-2015

A. Hodgson and S. Haq, Water adsorption and the wetting of metal surfaces, Surface Science Reports, vol.64, issue.9, pp.381-451, 2009.
DOI : 10.1016/j.surfrep.2009.07.001

J. Carrasco, A. Hodgson, and A. Michaelides, A molecular perspective of water at metal interfaces, Nature Materials, vol.93, issue.8, pp.667-674, 2012.
DOI : 10.1103/PhysRevLett.93.116101

S. J. Cox, S. M. Kathmann, B. Slater, and A. Michaelides, Molecular simulations of heterogeneous ice nucleation. I. Controlling ice nucleation through surface hydrophilicity, The Journal of Chemical Physics, vol.142, issue.18, p.184704, 2015.
DOI : 10.1016/j.jcat.2006.02.016

G. J. Martyna, M. L. Klein, and M. Tuckerman, Nos?????Hoover chains: The canonical ensemble via continuous dynamics, The Journal of Chemical Physics, vol.97, issue.4, pp.2635-2643, 1992.
DOI : 10.1063/1.442716

S. Plimpton, Fast Parallel Algorithms for Short-Range Molecular Dynamics, Journal of Computational Physics, vol.117, issue.1, pp.1-19, 1995.
DOI : 10.1006/jcph.1995.1039

J. Wedekind and D. Reguera, Kinetic Reconstruction of the Free-Energy Landscape, The Journal of Physical Chemistry B, vol.112, issue.35, pp.11060-11063, 2008.
DOI : 10.1021/jp804014h

G. A. Tribello, M. Bonomi, D. Branduardi, C. Camilloni, and G. Bussi, PLUMED 2: New feathers for an old bird, Computer Physics Communications, vol.185, issue.2, pp.604-613, 2014.
DOI : 10.1016/j.cpc.2013.09.018

G. A. Tribello, F. Giberti, G. C. Sosso, M. Salvalaglio, and M. Parrinello, Analyzing and Driving Cluster Formation in Atomistic Simulations, Journal of Chemical Theory and Computation, vol.13, issue.3, pp.1317-1327, 2017.
DOI : 10.1021/acs.jctc.6b01073

A. Laio and M. Parrinello, Escaping free-energy minima, Proc. Natl Acad. Sci. USA 99, pp.12562-12566, 2002.
DOI : 10.1126/science.220.4598.671

URL : http://www.pnas.org/content/99/20/12562.full.pdf

A. Barducci, G. Bussi, and M. Parrinello, Well-Tempered Metadynamics: A Smoothly Converging and Tunable Free-Energy Method, Physical Review Letters, vol.100, issue.2, p.20603, 2008.
DOI : 10.1021/jp067873l

D. Branduardi, F. L. Gervasio, and M. Parrinello, From A to B in free energy space, The Journal of Chemical Physics, vol.126, issue.5, p.54103, 2007.
DOI : 10.1063/1.479860

G. A. Gallet and F. Pietrucci, Structural cluster analysis of chemical reactions in solution, The Journal of Chemical Physics, vol.139, issue.7, p.74101, 2013.
DOI : 10.1103/PhysRevLett.107.085504

S. Pipolo, Navigating at Will on the Water Phase Diagram, Physical Review Letters, vol.119, issue.24
DOI : 10.1073/pnas.1100752108

P. Tiwary and M. Parrinello, A Time-Independent Free Energy Estimator for Metadynamics, The Journal of Physical Chemistry B, vol.119, issue.3, pp.736-742, 2014.
DOI : 10.1021/jp504920s

P. G. Bolhuis, D. Chandler, C. Dellago, and P. L. Geissler, : Throwing Ropes Over Rough Mountain Passes, in the Dark, Annual Review of Physical Chemistry, vol.53, issue.1, pp.291-318, 2002.
DOI : 10.1146/annurev.physchem.53.082301.113146

A. We, T. T. Li, G. Tribello, and S. J. , Cox for comments and suggestions. This work was supported by the European Research Council under the European Union's Seventh Framework Programme (FPERC Grant Agreement No. 616121 (HeteroIce project). A.M. is supported by the Royal Society through a Royal Society Wolfson Research Merit Award. We are grateful for computational resources provided by the London Center for Nanotechnology, the UCL Grace High Performance Computing Facility (Grace@UCL), the Materials Chemistry Consortium through the EPSRC Grant No. EP/L000202 and the UK Materials and Molecular Modeling Hub for computational resources, which is partially funded by EPSRC, This work was supported by French state funds managed by the ANR within the Investissements d'Avenir programme under reference ANR-11-IDEX-0004-02, within the framework of the cluster of excellence MATériaux Interfaces Surfaces Environnement (MATISSE) led by Sorbonne Universités, 2007.

M. F. Author, G. C. , and A. M. , conceived the research. M.F. performed the simulations and analysis. F.P. and S.P. contributed to the metadynamics simulations and analysis