Thermodynamic stability of hexagonal and cubic ices

The thermodynamic stability of hexagonal and cubic ices are examined by evaluating the free energies of those two phases over a wide range of temperature. One hundred proton-disordered configurations are generated for each form of ice, and a lattice dynamics calculation is applied. It is shown that the free energy of hexagonal ice is about 100 J mol−1 lower than that of cubic ice, and therefore more stable in the calculated temperature range (53–273 K). This is an agreement with experiment.

[1]  E. Clementi,et al.  Water–water interaction potential: An approximation of the electron correlation contribution by a functional of the SCF density matrix , 1984 .

[2]  E. Whalley,et al.  Cubic ice, snowflakes, and rare‐gas solids: Surface energy, entropy, and the stability of small crystals , 1984 .

[3]  Hideki Tanaka,et al.  A self-consistent phase diagram for supercooled water , 1996, Nature.

[4]  W. L. Jorgensen,et al.  Comparison of simple potential functions for simulating liquid water , 1983 .

[5]  S. Rice,et al.  Tests of effective pair potentials for water: Predicted ice structures , 1982 .

[6]  A. Hallbrucker,et al.  Calorimetric study of the vitrified liquid water to cubic ice phase transition , 1987 .

[7]  T. Straatsma,et al.  THE MISSING TERM IN EFFECTIVE PAIR POTENTIALS , 1987 .

[8]  Peter G. Wolynes,et al.  Large local energy fluctuations in water. II. Cooperative motions and fluctuations , 1988 .

[9]  Hideki Tanaka.  The thermodynamic stability of clathrate hydrate. III. Accommodation of nonspherical propane and ethane molecules , 1994 .

[10]  G. P. Johari.  The electrostatic field and the molecular dipole moment in the polymorphs of ice , 1984 .

[11]  D. Klug,et al.  Difference in energy between cubic and hexagonal ice , 1986 .

[12]  Effective pair potentials and the structure of ices VIII and IX , 1984 .

[13]  Walter Kauzmann,et al.  The Structure and Properties of Water , 1969 .

[14]  K. Pitzer,et al.  The Order-Disorder Problem for Ice , 1956 .

[15]  Robert H. Kincaid,et al.  Inclusion–exclusion calculation of the dipole–dipole energy of hexagonal ice and of cubic ice , 1993 .