Singularity-free interpretation of the thermodynamics of supercooled water

Physical Review E - Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics

Volumn 53, Issue 6 SUPPL. B, 1996, Pages 6144-6154

  Sastry, Srikanth ^a,b   Debenedetti, Pablo G ^b   Sciortino, Francesco ^c   Stanley, H E ^d  

^a NATIONAL INSTITUTES OF HEALTH   (United States)

^b Princeton University   (United States)

^c UNIVERSITÀ DI ROMA LA SAPIENZA   (Italy)

^d Boston University   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001101089     PISSN: 1063651X     EISSN: None     Source Type: Journal    
DOI: 10.1103/physreve.53.6144     Document Type: Article

References (37)

1. R. J. Speedy, J. Phys. Chem. 86, 982 (1982).
2. R. J. Speedy, J. Phys. Chem. 86, 3002 (1982).
3. P. G. Debenedetti and M. C. D'Antonio, J. Chem. Phys. 84, 3339 (1986).
4. P. G. Debenedetti and M. C. D'Antonio, J. Chem. Phys. 85, 4005 (1986).
5. M. C. D'Antonio and P. G. Debenedetti, J. Chem. Phys. 86, 2229 (1987).
6. P. G. Debenedetti and M. C. D'Antonio, AIChE J. 34, 447 (1988).
7. P. H. Poole, F. Sciortino, U. Essmann, and H. E. Stanley, Nature 360, 324 (1992); For recent related work, see also P. H. Poole, F. Sciortino, T. Grande, H. E. Stanley, and C. A. Angell, Phys. Rev. Lett. 73, 1632 (1994); H. Tanaka, Nature 380, 328 (1996).
8. P. H. Poole, F. Sciortino, U. Essmann, and H. E. Stanley, Nature 360, 324 (1992); For recent related work, see also P. H. Poole, F. Sciortino, T. Grande, H. E. Stanley, and C. A. Angell, Phys. Rev. Lett. 73, 1632 (1994); H. Tanaka, Nature 380, 328 (1996).
9. P. H. Poole, F. Sciortino, U. Essmann, and H. E. Stanley, Nature 360, 324 (1992); For recent related work, see also P. H. Poole, F. Sciortino, T. Grande, H. E. Stanley, and C. A. Angell, Phys. Rev. Lett. 73, 1632 (1994); H. Tanaka, Nature 380, 328 (1996).
10. P. H. Poole, F. Sciortino, U. Essmann, and H. E. Stanley, Phys. Rev. E 48, 3799 (1993).
11. In this paper, we refer to this behavior whereby the slope of the TMD changes sign as the retracing TMD behavior, and we call the thermodynamic scenarios consistent with this behavior retracing TMD scenarios.
12. P. H. Poole, U. Essmann, F. Sciortino, and H. E. Stanley, Phys. Rev. E 48, 4605 (1993).
13. O. Mishima, L. D. Calvert, and E. Whalley, Nature 310, 393 (1984).
14. O. Mishima, L. D. Calvert, and E. Whalley, Nature 314, 76 (1985).
15. O. Mishima, J. Chem. Phys. 100, 5910 (1994).
16. M. A. Floriano, Y. P. Handa, D. D. Klug, and E. Whalley, J. Chem. Phys. 91, 7187 (1993).
17. T. L. Hill, Statistical Mechanics (Dover Publications, New York, 1987).
18. C.
19. T is an increasing function of temperature.
20. D. H. Rasmussen, A. P. Mackenzie, C. A. Angell, and J. C. Tucker, Science 181, 342 (1973); C. A. Angell, J. Shuppert, and J. C. Tucker, J. Phys. Chem. 77, 3092 (1973).
21. D. H. Rasmussen, A. P. Mackenzie, C. A. Angell, and J. C. Tucker, Science 181, 342 (1973); C. A. Angell, J. Shuppert, and J. C. Tucker, J. Phys. Chem. 77, 3092 (1973).
22. The model does not prove that there are no low temperature singularities in water; only experiments can do that. Because such experiments must probe the behavior of a highly supercooled liquid, they are especially difficult. Given this situation, theoretical calculations are useful in two ways. First, they provide thermodynamically consistent scenarios with stringent constraints on the allowed behavior of observable quantities (e.g., a negatively-sloped TMD implies that the compressibility must increase upon cooling). Second, they suggest what must be measured in order to test the theoretical predictions. For example, volumetric and calorimetric measurements of glassy water at different pressures will yield information on the continuity of states between supercooled and glassy water, and hence on the presence, or absence, of the proposed spinodal, critical point, etc.
23. S. Sastry, F. Sciortino, and H.E. Stanley, J. Chem. Phys. 98, 9863 (1993).
24. M. Sasai, J. Chem. Phys. 93, 7329 (1990); Bull. Chem. Soc. Jpn. 97, 6292 (1993).
25. M. Sasai, J. Chem. Phys. 93, 7329 (1990); Bull. Chem. Soc. Jpn. 97, 6292 (1993).
26. S. S. Borick, P. G. Debenedetti, and S. Sastry, J. Phys. Chem. 99, 3781 (1995).
27. The absence of a second critical point, however, is not just an artifact of the mean field calculation, but a feature of the model.
28. This value corresponds to the percolation threshold of four bonded molecules on an ice lattice [30], which plays a special role in the percolation model of Stanley and Teixeira [29].
29. Y. Xie, K. F. Ludwig, Jr., G. Morales, D. E. Hare, and C. M. Sorensen, Phys. Rev. Lett. 71, 2050 (1993).
30. Y. Tsuchiya, J. Phys. Soc. Jpn. 60, 227 (1991).
31. Y. Tsuchiya, J. Phys. Soc. Jpn. 60, 960 (1991).
32. Y. Tsuchiya, J. Phys. Condens. Matter 3, 3163 (1991).
33. H. E. Stanley and J. Teixeira, J. Chem. Phys. 73, 3404 (1980).
34. R. L. Blumberg, H. E. Stanley, A. Geiger, and P. Mausbach, J. Chem. Phys. 80, 5230 (1984).
35. An example would be volumetric and calorimetric measurements of glassy water at different pressures; these yield data on the continuity of states between supercooled and glassy water that validate or falsify the scenario described by this model.
36. P. Gallo, F. Sciortino, P. Tartaglia, and S. -H. Chen (unpublished).
37. W. Götze and L. Sjögren, Rep. Prog. Phys. 55, 241 (1992).