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A universal origin for secondary relaxations in supercooled liquids and structural glasses

Nature Physics volume 6, pages 62–68 (2010)Cite this article

An Erratum to this article was published on 03 March 2015

This article has been updated

Abstract

Supercooled liquids and glasses show a range of relaxation times. Nearly all glass-forming liquids show secondary relaxations, high-frequency dynamical modes of structural reconfiguration seemingly distinct from the primary alpha relaxations. We show that accounting for driving-force fluctuations and the diversity of reconfiguring shapes in the random first-order transition theory yields a new dynamical process that shares many of the features ascribed to secondary relaxations. Whereas primary relaxation takes place through activated events involving compact regions, secondary relaxation is governed by more ramified, string-like or percolation-like clusters of particles. These secondary relaxations generate a low free-energy tail on the distribution of activation barriers, which becomes more prominent with increasing temperature. The activation barrier distributions of the two processes merge near the dynamical-crossover temperature Tc, where the secondary process ultimately becomes the dominant mode of structural relaxation. These string-like reconfigurations are seen to smooth the transition at Tc between high-temperature collisional dynamics and activated events.

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Figure 1: Disordered free-energy profiles showing the free-energy cost of rearranging a region with Nc compact particles and Nf stringy particles.
Figure 2: Activation-barrier distribution for free-energy barriers governing relaxation events in supercooled liquids.
Figure 3: Activation-barrier distribution for strong liquid with ΔCP≈1 kB per bead.
Figure 4: Activation-barrier distribution for fragile liquids with ΔCP≈3 kB per bead.
Figure 5: Relative importance of the secondary process to the total relaxation.
Figure 6: Activation-barrier distribution for secondary relaxation calculated from the statistical sampling of the fuzzy-sphere model with fluctuations.

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Change history

  • 18 February 2015

    In the version of this Article originally published the equation for the distribution of free energy barriers, which follows equation 4, was incorrect and should have read:

    . This error has now been corrected in the online versions of the Article.

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Acknowledgements

Support from NSF grant CHE0317017 and NIH grant 5R01GM44557 is gratefully acknowledged. Discussions on this topic with V. Lubchenko, H. Frauenfelder and J. Schmalian are gratefully acknowledged.

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Authors and Affiliations

  1. Department of Physics and Department of Chemistry and Biochemistry, Center for Theoretical Biological Physics, University of California at San Diego, La Jolla, California 92093, USA

    Jacob D. Stevenson & Peter G. Wolynes

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  1. Jacob D. Stevenson
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Contributions

The authors together conceived and implemented the theory and wrote the paper. J.D.S. implemented the numerical work.

Corresponding author

Correspondence to Peter G. Wolynes.

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Stevenson, J., Wolynes, P. A universal origin for secondary relaxations in supercooled liquids and structural glasses. Nature Phys 6, 62–68 (2010). https://doi.org/10.1038/nphys1432

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