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Universal scaling between structural relaxation and vibrational dynamics in glass-forming liquids and polymers

Nature Physics volume 4, pages 42–45 (2008)Cite this article

Abstract

If liquids, polymers, bio-materials, metals and molten salts can avoid crystallization during cooling or compression, they freeze into a microscopically disordered solid-like state, a glass1,2. On approaching the glass transition, particles become trapped in transient cages—in which they rattle on picosecond timescales—formed by their nearest neighbours; the particles spend increasing amounts of time in their cages as the average escape time, or structural relaxation time τα, increases from a few picoseconds to thousands of seconds through the transition. Owing to the huge difference between relaxation and vibrational timescales, theoretical3,4,5,6,7,8,9 studies addressing the underlying rattling process have challenged our understanding of the structural relaxation. Numerical10,11,12,13 and experimental studies on liquids14 and glasses8,15,16,17,18,19 support the theories, but not without controversies20 (for a review see ref. 21). Here we show computer simulations that, when compared with experiments, reveal the universal correlation of the structural relaxation time (as well as the viscosity η) and the rattling amplitude from glassy to low-viscosity states. According to the emerging picture the glass softens when the rattling amplitude exceeds a critical value, in agreement with the Lindemann criterion for the melting of crystalline solids22 and the free-volume model23.

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Figure 1: MD simulations of the polymer melt.
Figure 2: The structural relaxation time τα versus the DW factor 〈u2〉 from MD simulations for different chain lengths.
Figure 3: Scaling of the structural relaxation time τα (in MD units) versus the reduced mean square amplitude .

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Acknowledgements

The authors acknowledge discussions with C. A. Angell, S. Capaccioli, G. Carini, P. G. Debenedetti, J. Dyre, A. Fontana, K. L. Ngai, G. Ruocco, F. Sciortino and S. N. Shore. A. Wischnewski is thanked for providing the DW data of silica. Computational resources by ‘Laboratorio per il Calcolo Scientifico’ (Physics Department, University of Pisa) and financial support from MIUR within the PRIN project ‘Aging, fluctuation and response in out-of-equilibrium glassy systems’ are acknowledged.

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  1. L. Larini

    Present address: Present address: Center for Biological Modeling and Simulation, University of Utah, Salt Lake City, Utah 84112-0850, USA,

Authors and Affiliations

  1. Dipartimento di Fisica ‘Enrico Fermi’, Università di Pisa, Largo B. Pontecorvo 3, I-56127 Pisa, Italy

    L. Larini, A. Ottochian & D. Leporini

  2. Dipartimento di Fisica, Università di Roma, ‘La Sapienza’ Piazzale Aldo Moro, 2, 00185 Rome, Italy

    C. De Michele

  3. INFM-CRS Soft, Piazzale Aldo Moro 2, 00185 Roma, Italy

    C. De Michele & D. Leporini

Authors
  1. L. Larini
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  2. A. Ottochian
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Corresponding author

Correspondence to D. Leporini.

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Simulations and Experimental data and scaling (PDF 139 kb)

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Larini, L., Ottochian, A., De Michele, C. et al. Universal scaling between structural relaxation and vibrational dynamics in glass-forming liquids and polymers. Nature Phys 4, 42–45 (2008). https://doi.org/10.1038/nphys788

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