We report a lattice-dynamics study of relative
stability of various phases of natural silicates MSiO4
(M =Zr, Hf, Th, and U as a function of pressure (P)
and temperature (T), which is important in the context of
their use in nuclear waste storage media. Extending our previous
work on ZrSiO4, the Gibbs free energy has been
calculated using a transferable interatomic potential in various
phases over a range of P and T. Due to an
interesting interplay between the vibrational entropy and atomic
packing, the zircon body-centered tetragonal, I41/amd),
scheelite body-centered tetragonal, I41/a),
and huttonite (monoclinic, P21/n) phases
occur at different P and T. It is shown that, for
ThSiO4 at high P, the huttonite and scheelite
phases are favored at high and low T, respectively.
However, for both USiO4 and HfSiO4 the
huttonite phase is dynamically unstable and the scheelite phase
is stable as the high pressure phase. In fact, the calculations
reveal that the stability of the huttonite phase is determined
by the ionic size of the M atom; this phase is unstable
for the silicate with the smaller Hf and U ions, and stable with
the larger Th ion. The calculated phase diagrams are in fair
agreement with the reported experimental observations. The
calculated structures, phonon spectra, and various thermodynamic
properties also fairly well reproduce the available experimental
data. The low-energy phonons in the huttonite phase that
contribute to its large vibrational entropy are found to involve
librational motion of the silicate tetrahedral units.
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