Phase transitions in confined water nanofilms

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Abstract

Bulk water has three phases: solid, liquid and vapour. In addition to undergoing a phase transition (of the first order) between them, liquid and vapour can deform continuously into each other without crossing a transition line—in other words, there is no intrinsic distinction between the two phases. Hence, the first-order line of the liquid–vapour phase transition should terminate at a critical point. In contrast, the first-order transition line between solid and liquid is believed to persist indefinitely without terminating at a critical point1. In recent years, however, it was reported that inside carbon nanotubes, freezing of water may occur continuously as well as discontinuously through a first-order phase transition2. Here we present simulation results for water in a quasi-two-dimensional hydrophobic nanopore slit, which are consistent with the idea that water may freeze by means of both first-order and continuous phase transitions. Our results lead us to hypothesize the existence of a connection point at which first-order and continuous transition lines meet3,4.

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Figure 1: Discontinuous versus continuous behaviour of potential energy below and above the critical density.
Figure 2: Lateral oxygen–oxygen RDF gOOxy and TDP ρz at various temperatures.
Figure 3: Two different ice structures below and above the critical density.
Figure 4: Log–log plot of the time evolution of the lateral MSD Δx y at several temperatures and density ρ=1.33 g cm−3 (>ρc).
Figure 5: Schematic phase diagram of confined water in the density–temperature (ρT) plane, estimated from behaviours of the potential energy, RDF, TDP and MSD.

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Acknowledgements

We thank S. V. Buldyrev for helpful discussions. S.H., P.K. and H.E.S. acknowledge support from NSF Grant No. CHE 0606489 and the Keck Foundation NAKFI award. M.Y.C. acknowledges support from NRF through the Basic Science Research Program (2009–0080791).

Author information

S.H., M.Y.C., P.K. and H.E.S. designed the research; S.H. carried out simulations; and S.H., M.Y.C., P.K. and H.E.S. analysed data and wrote the paper.

Correspondence to Sungho Han.

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Han, S., Choi, M., Kumar, P. et al. Phase transitions in confined water nanofilms. Nature Phys 6, 685–689 (2010) doi:10.1038/nphys1708

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