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Generic mechanism for generating a liquid–liquid phase transition

Nature volume 409, pages 692–695 (2001)Cite this article

Abstract

Recent experimental results1 indicate that phosphorus—a single-component system—can have a high-density liquid (HDL) and a low-density liquid (LDL) phase. A first-order transition between two liquids of different densities2 is consistent with experimental data for a variety of materials3,4, including single-component systems such as water5,6,7,8, silica9 and carbon10. Molecular dynamics simulations of very specific models for supercooled water2,11, liquid carbon12 and supercooled silica13 predict a LDL–HDL critical point, but a coherent and general interpretation of the LDL–HDL transition is lacking. Here we show that the presence of a LDL and a HDL can be directly related to an interaction potential with an attractive part and two characteristic short-range repulsive distances. This kind of interaction is common to other single-component materials in the liquid state (in particular, liquid metals2,14,15,16,17,18,19,20,21), and such potentials are often used to describe systems that exhibit a density anomaly2. However, our results show that the LDL and HDL phases can occur in systems with no density anomaly. Our results therefore present an experimental challenge to uncover a liquid–liquid transition in systems like liquid metals, regardless of the presence of a density anomaly.

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Figure 1: Pressure-density isotherms, crystallization line and spinodal line from the molecular dynamics simulations for the isotropic pair potential in three dimensions.
Figure 2: The phase diagrams, with coexistence lines and critical points resulting from MD simulations.

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Acknowledgements

We wish to thank L. A. N. Amaral, P. V. Giaquinta, E. La Nave, T. Lopez Ciudad, S. Mossa, G. Pellicane, A. Scala, F. W. Starr, J. Teixeira, and, in particular, F. Sciortino for helpful suggestions and discussions. We thank the NSF and the CNR (Italy) for partial support.

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Authors and Affiliations

  1. Center for Polymer Studies and Department of Physics, Boston University, Boston, 02215, Massachusetts, USA

    Giancarlo Franzese, Anna Skibinsky, Sergey V. Buldyrev & H. Eugene Stanley

  2. Dipartimento di Fisica, Università di Messina and Istituto Nazionale Fisica della Materia, 98166, Messina, Italy

    Gianpietro Malescio

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  1. Giancarlo Franzese
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Correspondence to Giancarlo Franzese.

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Franzese, G., Malescio, G., Skibinsky, A. et al. Generic mechanism for generating a liquid–liquid phase transition. Nature 409, 692–695 (2001). https://doi.org/10.1038/35055514

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