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Liquids more stable than crystals in particles with limited valence and flexible bonds

Nature Physics volume 9, pages 554–558 (2013)Cite this article

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Abstract

All liquids (except helium owing to quantum effects) crystallize at low temperatures, forming ordered structures. The competition between disorder, which stabilizes the liquid phase, and energy, which leads to a preference for the crystalline structure, inevitably favours the crystal when the temperature is lowered and entropy becomes progressively less relevant. The liquid state survives at low temperatures only as a glass, an out-of-equilibrium arrested state of matter. This textbook description holds inevitably for atomic and molecular systems, where particle interactions are set by quantum-mechanical laws. The question remains whether it holds for colloidal particles, where interparticle interactions are usually short-ranged and tunable. Here we show that for patchy colloids with limited valence1, conditions can be found for which the liquid phase is stable even in the zero-temperature limit. Our results offer fresh cues for understanding the stability of gels2 and the glass-forming ability of molecular network glasses3,4.

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Figure 1: Phase diagram of patchy colloids for different patch widths.
Figure 2: Number of bonds per particle in the tetrahedral liquid phase.
Figure 3: Total, vibrational and configurational entropy for the zero-temperature phases.
Figure 4: Defects in the tetrahedral network and their dynamic role.

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Acknowledgements

We acknowledge support from ERC-226207-PATCHYCOLLOIDS and MIUR-PRIN. We thank F. Romano for useful discussions.

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Authors and Affiliations

  1. Department of Physics, Sapienza, Universitá di Roma, Piazzale Aldo Moro 2, Roma, I-00185, Italy

    Frank Smallenburg & Francesco Sciortino

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  1. Frank Smallenburg
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  2. Francesco Sciortino
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Contributions

F. Sciortino suggested the study. F. Sciortino and F. Smallenburg designed the research. F. Smallenburg performed the simulations and the data analysis. F. Sciortino and F. Smallenburg contributed to the interpretation of the results and to the writing of the paper.

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Correspondence to Frank Smallenburg.

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The authors declare no competing financial interests.

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Smallenburg, F., Sciortino, F. Liquids more stable than crystals in particles with limited valence and flexible bonds. Nature Phys 9, 554–558 (2013). https://doi.org/10.1038/nphys2693

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