Hostname: page-component-586b7cd67f-g8jcs Total loading time: 0 Render date: 2024-11-25T18:29:06.956Z Has data issue: false hasContentIssue false
  • English
  • Français

Metastable Melting Lines for H2O and the Liquid-Liquid Phase Transition Hypothesis

Published online by Cambridge University Press:  10 February 2011

Osamu Mishima  and
H. Eugene Stanley
Osamu Mishima
Affiliation:
Nat'l Inst. for Research in Inorganic Materials, 1–1 Namiki, Tsukuba, Ibaraki 305, Japan
H. Eugene Stanley
Affiliation:
Center for Polymer Studies and Dept. of Physics, Boston Univ., Boston, MA 02215 USA
Get access

Abstract

When ice Ih in an emulsion is compressed below 250 K, it melts to supercooled liquid water, avoiding the formation of other crystal phases. Here, we create emulsified high-pressure ices under high pressure and low temperature, and measure their temperature while these ices are decompressed at a constant rate at different temperatures. We detect metastable melting points of high-pressure ices, and identify their melting lines. We find what could be possibly two new ice phases, and discuss the relationship between decompression-induced melting and decompression-induced amorphization. Finally, we discuss briefly the analysis of experimental data and simulation results that are consistent with the hypothesized “second critical point” with temperature and pressure coordinates of approximately 200 K and 100 Mpa.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 499: Symposium DD – High Pressure Materials Research , 1997 , 443
Copyright
Copyright © Materials Research Society 1998

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

[1] Mishima, O., Nature 384, 546 (1996).Google Scholar
[2] Kanno, H., Speedy, R., and Angell, C. A., Science 189, 880 (1975).Google Scholar
[3] Bridgman, P. W., Proc. Amer. Acad. Arts Sci. 47, 441 (1912).Google Scholar
[4] Evans, L. F., J. Appl. Phys. 38, 4930 (1967).Google Scholar
[5] Klug, D. D., Honda, Y. P., Tse, J. S., and Whalley, E., J. Chem. Phys. 90, 2390 (1989).Google Scholar
[6] Mishima, O., J. Chem. Phys. 100, 5910 (1994).Google Scholar
[7] Mishima, O. and Stanley, H. E., in Intl. Conf. High Pressure Sci. Tech.: AIRAPT, Kyoto (August 1997), in press.Google Scholar
[8] Mishima, O. and Stanley, H. E., Nature 392, 164 (1998);Google Scholar
Debenedetti, P., Nature 392, 127 (1998).Google Scholar
[9] Poole, P. H., Sciortino, F., Essmann, U. and Stanley, H. E., Nature 360, 324 (1992).Google Scholar
[10] Poole, P. H., Sciortino, F., Grande, T., Stanley, H. E. and Angell, C. A., Phys. Rev. Lett. 73, 1632 (1994).Google Scholar
[11] Boriek, S. S., Debenedetti, P. G. and Sastry, S., J. Phys. Chem. 99, 3781 (1995).Google Scholar
[12] Tanaka, H., Nature 380, 328 (1996).Google Scholar
[13] Tanaka, H., J. Chem. Phys. 105, 5099 (1996).Google Scholar
[14] Roberts, C. J., Panagiotopoulos, A. Z. and Debenedetti, P. G., Phys. Rev. Lett. 77, 4386 (1996).Google Scholar
[15] Sastry, S., Debenedetti, P. G., Sciortino, F., and Stanley, H. E., Phys. Rev. E 53, 6144 (1996).Google Scholar
[16] Harrington, S., Zhang, R., Poole, P. H., Sciortino, F. and Stanley, H. E., Phys. Rev. Lett. 78, 2409 (1997).Google Scholar
[17] Harrington, S., Poole, P. H., Sciortino, F. and Stanley, H. E., J. Chem. Phys. 107, 7443 (1997).Google Scholar
[18] Shiratani, E. and Sasai, M., J. Chem. Phys 108, 3264 (1998).Google Scholar
[19] Stanley, H. E., Cruz, L., Harrington, S. T., Poole, P. H., Sastry, S., Sciortino, F., Starr, F. W., and Zhang, R., Physica A 236, 19 (1997).Google Scholar
[20] Stanley, H. E., Harrington, S. T., Mishima, O., Poole, P. H., and Sciortino, F., “Cooperative Molecular Motions in Water: The Second Critical Point Hypothesis” Intl. Conf. High Pressure Sci. Tech.: AIRAPT, Kyoto (August 1997), in press.Google Scholar
[21] Lang, E. and Lüdemann, H.-D., Ber. Bunsenges. Phys. Chem. 84, 462 (1980).Google Scholar
[22] Lang, E. and Lüdemann, H.-D., Ber. Bunsenges. Phys. Chem. 85, 1016 (1981).Google Scholar
[23] Lang, E. and Lüdemann, H.-D., J. Chem. Phys. 67, 718 (1977).Google Scholar
[24] Lang, E. and Lüdemann, H.-D., in NMR Basic Principles and Progress, Vol. 24 (Springer-Verlag, Berlin, 1990), pp. 131–187.Google Scholar
[25]This extrapolation is made by eye, not by formula. The extrapolated inflection corresponds to occurrence of a singularity or critical point. This occurs at roughly the same coordinates as found in the experiments reported in Ref. [8], and so is consistent with (but of course does not prove) the hypothesized critical point.Google Scholar
[26] This tetrahedrality of local structure has the implication that locally-ordered regions of the liquid will have a larger specific volume rather than a smaller specific volume than the global specific volume (as in most liquids, for which the local structure, also resembling the global structure of the solid, has a smaller specific volume than the global specific volume. The coefficient of thermal expansion is proportional to the correlation function of σS and σV (where S is the entropy, V the specific volume, and σ denotes the deviation of the local value of a quantity from its global value). Hence whenever we are at a state point in the P-T phase diagram to the left of the locus of points where the coefficient of thermal expansion is zero (the “TMD line”), then of necessity the volume fluctuations are most unusual in that they are anticorrelated with the entropy fluctuations. These unusual fluctuations grow as one moves further into this “anomalous” region (to the left of the TMD line), and ultimately a new phase condenses out of the fluid which has the property that although the entropy of the new phase is low, the specific volume is large-this is what is called the “low-density liquid.” Since other tetrahedral liquids have similar features, we might anticipate similar critical points occur on the liquid free energy surface of these liquids. Simulation evidence in favor of this possibility has been reported recently.Google Scholar
Poole, P. H., Hemmati, M. and Angeli, C. A., Phys. Rev. Lett. 79, 2281 (1997).Google Scholar