Abstract
Some liquids do not crystallize below the melting point, but instead enter into a supercooled state and on cooling eventually become a glass at the glass-transition temperature. During this process, the liquid dynamics not only drastically slow down, but also become progressively more heterogeneous. The relationship between the kinetic slowing down and growing dynamic heterogeneity is a key problem of the liquid–glass transition. Here, we study this problem by using a liquid model, with a crystalline ground state, for which we can systematically control frustration against crystallization. We found that slow regions having a high degree of crystalline order emerge below the melting point, and their characteristic size and lifetime increase steeply on cooling. These crystalline regions lead to dynamic heterogeneity, suggesting a connection to the complex free-energy landscape and the resulting slow dynamics. These findings point towards an intrinsic link between the glass transition and crystallization.
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References
Sillescu, H. Heterogeneity at the glass transition: a review. J. Non-Cryst. Solids 243, 81–108 (1999).
Ediger, M. D. Spatially heterogeneous dynamics in supercooled liquids. Annu. Rev. Phys. Chem. 51, 99–128 (2000).
Angell, C. A., Ngai, K., McKenna, G. B., McMillan, P. F. & Martin, S. W. Relaxation in glassforming liquids and amorphous solids. J. Appl. Phys. 88, 3113–3157 (2000).
Richert, R. Heterogeneous dynamics in liquids: fluctuations in space and time. J. Phys. Condens. Matter 14, R703–R738 (2002).
Debenedetti, P. G. & Stillinger, F. H. Supercooled liquids and the glass transition. Nature 410, 259–267 (2001).
Andersen, H. C. Molecular dynamics studies of heterogeneous dynamics and dynamic crossover in supercooled atomic liquids. Proc. Natl Acad. Sci. USA 102, 6686–6691 (2005).
Adam, G. & Gibbs, J. H. On the temperature dependence of cooperative relaxation properties in glass-forming liquids. J. Chem. Phys. 43, 139–146 (1965).
Kirkpatrick, T. R., Thirumalai, D. & Wolynes, P. G. Scaling concepts for the dynamics of viscous liquids near an ideal glassy state. Phys. Rev. A 40, 1045–1054 (1989).
Xia, X. & Wolynes, P. G. Microscopic theory of heterogeneity and nonexponential relaxations in supercooled liquids. Phys. Rev. Lett. 86, 5526–5529 (2001).
Toninelli, C., Wyart, M., Berthier, L., Biroli, G. & Bouchaud, J.-P. Dynamical susceptibility of glass formers: Contrasting the predictions of theoretical scenarios. Phys. Rev. E 71, 041505 (2005).
Garrahan, J. P. & Chandler, D. Coarse-grained microscopic model of glass formers. Proc. Natl Acad. Sci. USA 100, 9710–9714 (2003).
Tarjus, G., Kivelson, S. A., Nussinov, Z. & Viot, P. The frustration-based approach of supercooled liquids and the glass transition: a review and critical assessment. J. Phys. Condens. Matter 17, R1143–R1182 (2005).
Frank, F. C. Supercooling of liquids. Proc. R. Soc. Lond. A 215, 43–46 (1952).
Steinhardt, P. J., Nelson, D. R. & Ronchetti, M. Bond-orientational order in liquids and glasses. Phys. Rev. B 28, 784–805 (1983).
Dzugutov, M. Glass formation in a simple monatomic liquid with icosahedral inherent local order. Phys. Rev. A 46, R2984–R2987 (1992).
Doye, J. P., Wales, D. J., Zetterling, F. H. & Dzugutov, M. The favored cluster structures of model glass formers. J. Chem. Phys. 118, 2792–2799 (2003).
Tanaka, H. Two-order-parameter description of liquids: I. A general model of glass transition covering its strong to fragile limit. J. Chem. Phys. 111, 3163–3174 (1999).
Tanaka, H. Roles of local icosahedral chemical ordering in glass and quasicrystal formation in metallic glass formers. J. Phys. Condens. Matter 15, L491–L498 (2003).
Tanaka, H. Two-order-parameter model of the liquid-glass transition: I. Relation between glass transition and crystallization. J. Non-Cryst. Solids 351, 3371–3384 (2005).
Tanaka, H. Simple physical model of liquid water. J. Chem. Phys. 112, 799–809 (2000).
Widmer-Cooper, A., Harrowell, P. & Fynewever, H. How reproducible are dynamic heterogeneities in a supercooled liquid? Phys. Rev. Lett. 93, 135701 (2004).
Goldstein, M. Viscous liquids and the glass transition: A potential energy barrier picture. J. Chem. Phys. 51, 3728–3739 (1969).
Sciortino, F. Potential energy landscape description of supercooled liquids and glasses. J. Stat. Mech. P05015 (2005).
Sastry, S., Debenedetti, P. G. & Stillinger, F. H. Signatures of distinct dynamical regimes in the energy landscape of a glass-forming liquid. Nature 393, 554–557 (1998).
Stillinger, F. H. & Weber, T. A. Hidden structure in liquids. Phys. Rev. A 25, 978–989 (1982).
Lačević, N., Starr, F. W., Schrøder, T. B. & Glotzer, S. C. Spatially heterogeneous dynamics investigated via a time-dependent four-point density correlation function. J. Chem. Phys. 119, 7372–7387 (2003).
Eckstein, E. et al. X-ray scattering study and molecular simulation of glass forming liquids: Propylene carbonate and salol. J. Chem. Phys. 113, 4751–4762 (2000).
Sturgeon, J. B. & Laird, B. B. Symplectic algorithm for constant-pressure molecular dynamics using a Nosé–Poincaré thermostat. J. Chem. Phys. 112, 3474–3482 (2000).
Acknowledgements
The authors are grateful to C. P. Royall for a critical reading of our manuscript. This work was partially supported by a grand-in-aid from the Ministry of Education, Culture, Sports, Science and Technology, Japan.
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Supplementary information
Supplementary Information, Video S1
Temporal change in the medium-range crystalline order and dynamic heterogeneity. A movie of liquid structures having crystalline mediumrange order at T=0.18 and Δ=0.6, which corresponds to Fig. 4b. The colouring in this Video is the same as that in Fig. 4b. This video covers the time duration of 3τα. (MOV 6847 kb)
Supplementary Information, Video S2
Temporal change in the medium-range crystalline order for T=0.17 and δ=0.6. The coloring in this Video is the same as that in Supplementary Figure 2. This movie covers from t=-3 τα to t=5 τα and thus includes the time span of Supplementary Figure 2. (MOV 2958 kb)
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Shintani, H., Tanaka, H. Frustration on the way to crystallization in glass. Nature Phys 2, 200–206 (2006). https://doi.org/10.1038/nphys235
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DOI: https://doi.org/10.1038/nphys235
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